TW201700999A - Polarizing plate, method of manufacturing the same, and optical display comprising the same - Google Patents

Polarizing plate, method of manufacturing the same, and optical display comprising the same Download PDF

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TW201700999A
TW201700999A TW105119019A TW105119019A TW201700999A TW 201700999 A TW201700999 A TW 201700999A TW 105119019 A TW105119019 A TW 105119019A TW 105119019 A TW105119019 A TW 105119019A TW 201700999 A TW201700999 A TW 201700999A
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adhesive layer
polarizing plate
polarizer
meth
adhesive
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TW105119019A
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TWI619975B (en
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鄭宇鎭
李承俊
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三星Sdi股份有限公司
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3025Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08Homopolymers or copolymers of acrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35Heat-activated
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14Protective coatings, e.g. hard coatings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/20Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/40Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/414Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2429/00Presence of polyvinyl alcohol
    • C09J2429/006Presence of polyvinyl alcohol in the substrate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of (meth)acrylic polymer

Abstract

A polarizing plate, a method of manufacturing the same, and an optical display including the same. The polarizing plate includes a polarizer and a first adhesive layer formed on a lower surface of the polarizer, wherein the first adhesive layer includes an adhesive resin having a glass transition temperature of about 50 DEG C or more and has a haze of about 1% or less at a wavelength of about 380 nm to about 780 nm.

Description

偏光板、偏光板的製造方法以及包括偏光板的光學顯示器Polarizing plate, manufacturing method of polarizing plate, and optical display including polarizing plate

本發明主張2015年6月18日在韓國智慧財產局提交的韓國專利申請第10-2015-0086942號的權益,所述專利申請以全文引用的方式併入本文中。The present invention claims the benefit of Korean Patent Application No. 10-2015-0086942, filed on June 18, 2015, in the Korean Intellectual Property Office, which is hereby incorporated by reference in its entirety.

本發明有關一種偏光板、一種偏光板製造方法以及一種包含偏光板的光學顯示器The present invention relates to a polarizing plate, a method of manufacturing a polarizing plate, and an optical display including the polarizing plate

向光學顯示器提供偏光板以防外部光反射,或使光源發出的光偏振。光學顯示器可以包含液晶顯示器、有機發光顯示器和可繞式有機發光顯示器。近年來,向光學顯示器施加量子點以便改進彩色再現和可視度。A polarizing plate is provided to the optical display to prevent external light from being reflected or to polarize light emitted from the light source. The optical display can include a liquid crystal display, an organic light emitting display, and a wrapable organic light emitting display. In recent years, quantum dots have been applied to optical displays to improve color reproduction and visibility.

近年來,通過僅僅在偏光鏡的一個表面上形成保護膜,藉此將偏光板製造成減小的厚度。僅僅在偏光鏡的一個表面上形成有保護膜的偏光板可能會由於外部濕氣穿透偏光鏡的另一個表面而遇到耐久性的降低,並且還可能在熱衝擊狀況下遇到偏光鏡的抗裂性的降低。為了解決這些問題,在偏光鏡的另一個表面上形成黏著層,使得偏光板可以經由黏著層固定到光學顯示器中的光學裝置,以便改進偏光板的耐久性和抗裂性。黏著層需要改進偏光板的耐久性和抗裂性,同時呈現良好的透明度以便用於光學顯示器中。另外,隨著可繞式顯示器近年來的發展,對於改進偏光板的可繞式的研究也在繼續。In recent years, the polarizing plate is manufactured to have a reduced thickness by forming a protective film only on one surface of the polarizing mirror. A polarizing plate in which a protective film is formed only on one surface of a polarizer may experience a decrease in durability due to external moisture penetrating the other surface of the polarizer, and may also encounter a polarizer under thermal shock conditions. Reduced crack resistance. In order to solve these problems, an adhesive layer is formed on the other surface of the polarizer so that the polarizing plate can be fixed to the optical device in the optical display via the adhesive layer in order to improve the durability and crack resistance of the polarizing plate. The adhesive layer needs to improve the durability and crack resistance of the polarizing plate while exhibiting good transparency for use in an optical display. In addition, with the development of the rewritable display in recent years, research on the rewritable method for improving the polarizing plate has continued.

日本專利公開案第2013-072951 A號等等中公開了本發明的背景技術。The background art of the present invention is disclosed in Japanese Patent Laid-Open Publication No. 2013-072951 A and the like.

根據本發明的一個方面,提供一種偏光板,所述偏光板包含偏光鏡和形成於所述偏光鏡的下表面上的第一黏著層,其中第一黏著層包含玻璃轉化溫度為大約50℃或更高的黏著性樹脂,並且第一黏著層在大約380奈米到大約780奈米的波長下的霧度為大約1%或更低。According to an aspect of the invention, there is provided a polarizing plate comprising a polarizer and a first adhesive layer formed on a lower surface of the polarizer, wherein the first adhesive layer comprises a glass transition temperature of about 50 ° C or A higher adhesive resin, and the first adhesive layer has a haze of about 1% or less at a wavelength of from about 380 nm to about 780 nm.

根據本發明的一實施例,第一黏著層可更包括用脲基甲酸酯基團改性後的聚異氰酸酯固化劑。According to an embodiment of the invention, the first adhesive layer may further comprise a polyisocyanate curing agent modified with an allophanate group.

根據本發明的一實施例,偏光板可更包括第二黏著層,其形成於第一黏著層的下表面上其中偏光板在大約380奈米到大約780奈米的波長下的霧度為大約1%或更低。According to an embodiment of the present invention, the polarizing plate may further include a second adhesive layer formed on a lower surface of the first adhesive layer, wherein a haze of the polarizing plate at a wavelength of about 380 nm to about 780 nm is about 1% or lower.

根據本發明的一實施例,偏光鏡的下表面可受到電暈處理、電漿處理和底塗劑處理中的至少一項處理。According to an embodiment of the invention, the lower surface of the polarizer may be subjected to at least one of corona treatment, plasma treatment, and primer treatment.

根據本發明的一實施例,第一黏著層可直接形成於偏光鏡的下表面上。According to an embodiment of the invention, the first adhesive layer may be formed directly on the lower surface of the polarizer.

根據本發明的一實施例,第一黏著層的拉伸模數根據ASTM D882測量可為大約10兆帕到小於大約2,000兆帕。According to an embodiment of the invention, the tensile modulus of the first adhesive layer may range from about 10 MPa to less than about 2,000 MPa as measured according to ASTM D882.

根據本發明的一實施例,第二黏著層的拉伸模數根據ASTM D882測量可低於第一黏著層。According to an embodiment of the invention, the tensile modulus of the second adhesive layer may be lower than the first adhesive layer as measured according to ASTM D882.

根據本發明的一實施例,用脲基甲酸酯基團改性後的聚異氰酸酯固化劑的存在量按100重量份的黏著性樹脂計可為大約5重量份到大約50重量份。According to an embodiment of the present invention, the polyisocyanate curing agent modified with the allophanate group may be present in an amount of from about 5 parts by weight to about 50 parts by weight per 100 parts by weight of the adhesive resin.

根據本發明的一實施例,用脲基甲酸酯基團改性後的聚異氰酸酯固化劑可包括用脲基甲酸酯基團改性後的四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、十二亞甲基二異氰酸酯和三甲基六亞甲基二異氰酸酯中的至少一種。According to an embodiment of the present invention, the polyisocyanate curing agent modified with the allophanate group may include tetramethylene diisocyanate modified with an allophanate group, hexamethylene di At least one of isocyanate, dodecyl diisocyanate, and trimethylhexamethylene diisocyanate.

根據本發明的一實施例,第一黏著層的厚度可為大約5微米到大約40微米。According to an embodiment of the invention, the first adhesive layer may have a thickness of from about 5 microns to about 40 microns.

根據本發明的一實施例,偏光板可更包括形成於偏光鏡的上表面上的保護層。According to an embodiment of the present invention, the polarizing plate may further include a protective layer formed on an upper surface of the polarizer.

根據本發明的一實施例,第二黏著層的拉伸模數根據ASTM D882測量可為大約0.01兆帕到小於大約1兆帕。According to an embodiment of the invention, the tensile modulus of the second adhesive layer may range from about 0.01 MPa to less than about 1 MPa as measured according to ASTM D882.

根據本發明的一實施例,第二黏著層的厚度大於所述第一黏著層。According to an embodiment of the invention, the second adhesive layer has a thickness greater than the first adhesive layer.

根據本發明的另一個方面,提供一種偏光板,所述偏光板包含偏光鏡和形成於所述偏光鏡的下表面上的第一黏著層,其中第一黏著層包含玻璃轉化溫度為大約50℃或更高的黏著性樹脂,以及用脲基甲酸酯基團改性後的聚異氰酸酯固化劑。According to another aspect of the present invention, there is provided a polarizing plate comprising a polarizer and a first adhesive layer formed on a lower surface of the polarizer, wherein the first adhesive layer comprises a glass transition temperature of about 50 ° C Or a higher adhesive resin, and a polyisocyanate curing agent modified with an allophanate group.

根據本發明的另一方面,提供一種偏光板,所述偏光板包含:偏光鏡;形成於偏光鏡的上表面上的保護層;形成於偏光鏡的下表面上的第一黏著層;以及形成於第一黏著層的下表面上的第二黏著層,其中所述第一黏著層包含玻璃轉化溫度為大約50℃或更高的黏著性樹脂,並且所述第一黏著層在大約380奈米到大約780奈米的波長下的霧度為大約1%或更低。According to another aspect of the present invention, a polarizing plate is provided, the polarizing plate comprising: a polarizing mirror; a protective layer formed on an upper surface of the polarizing mirror; a first adhesive layer formed on a lower surface of the polarizing mirror; and forming a second adhesive layer on a lower surface of the first adhesive layer, wherein the first adhesive layer comprises an adhesive resin having a glass transition temperature of about 50 ° C or higher, and the first adhesive layer is at about 380 nm The haze to a wavelength of about 780 nm is about 1% or less.

根據本發明的又一方面,提供一種製造偏光板的方法,其包含:同時塗布第二黏著層用的組成物和第一黏著層用的組成物,然後執行乾燥以形成堆疊結構,所述堆疊結構中包括第一黏著層用的薄片和第二黏著層用的薄片;將第一黏著層用的薄片與偏光鏡的一個表面層合;以及固化第二黏著層用的薄片和第一黏著層用的薄片。According to still another aspect of the present invention, a method of manufacturing a polarizing plate comprising: simultaneously coating a composition for a second adhesive layer and a composition for a first adhesive layer, and then performing drying to form a stacked structure, the stack The structure includes a sheet for the first adhesive layer and a sheet for the second adhesive layer; laminating the sheet for the first adhesive layer with one surface of the polarizer; and curing the sheet for the second adhesive layer and the first adhesive layer Used sheet.

根據本發明的一實施例,堆疊結構可包括第一黏著層用的薄片和依次堆疊在上面的第二黏著層用的薄片。According to an embodiment of the present invention, the stacked structure may include a sheet for the first adhesive layer and a sheet for the second adhesive layer stacked thereon in this order.

根據本發明的一實施例,在與第一黏著層用的薄片層合之前,偏光鏡的一個表面可受到電暈處理、電漿處理和底塗劑處理中的至少一項處理。According to an embodiment of the present invention, one surface of the polarizer may be subjected to at least one of corona treatment, plasma treatment, and primer treatment before laminating the sheet for the first adhesive layer.

根據本發明的一實施例,第一黏著層用的組成物可包括玻璃轉化溫度為50℃或更高的黏著性樹脂和用脲基甲酸酯基團改性後的聚異氰酸酯固化劑。According to an embodiment of the present invention, the composition for the first adhesive layer may include an adhesive resin having a glass transition temperature of 50 ° C or higher and a polyisocyanate curing agent modified with an allophanate group.

根據本發明的又一方面,提供一種包含如上文所闡述的偏光板的光學顯示器。According to yet another aspect of the present invention, an optical display comprising a polarizing plate as set forth above is provided.

本發明提供這樣一種偏光板,該偏光板包含僅僅形成在偏光鏡的一個表面上的保護層,並且在斷裂時或再加工時的惡劣條件下展現出良好的耐久性。本發明提供這樣一種偏光板,該偏光板包含僅僅形成在偏光鏡的一個表面上的保護層,並且在高溫和/或高濕度條件下或在熱衝擊條件下防止偏光鏡中產生開裂和/或偏光鏡的變色。本發明提供這樣一種偏光板,該偏光板包含僅僅形成在偏光鏡的一個表面上的保護層和具有高拉伸模數的黏著層,該黏著層是通過在不使用可熱固化起始劑的情況下的熱固化獲得的。本發明提供這樣一種偏光板,該偏光板包含僅僅形成在偏光鏡的一個表面上的保護層,並且展現出良好的可繞式以用於可繞式顯示器。The present invention provides a polarizing plate comprising a protective layer formed only on one surface of a polarizing mirror, and exhibiting good durability under severe conditions at the time of breaking or reworking. The present invention provides a polarizing plate comprising a protective layer formed only on one surface of a polarizing mirror, and preventing cracking and/or occurrence of cracking in a polarizing mirror under high temperature and/or high humidity conditions or under thermal shock conditions. The discoloration of the polarizer. The present invention provides a polarizing plate comprising a protective layer formed only on one surface of a polarizing mirror and an adhesive layer having a high tensile modulus by using a heat curable initiator In the case of thermal curing obtained. The present invention provides a polarizing plate comprising a protective layer formed only on one surface of a polarizing mirror, and exhibiting a good wrapable type for a wraparound display.

下文將參照附圖詳細描述本發明的實施例。應理解,本發明不限於以下實施例且可以用不同方式具體實施,且給出以下實施例是為了提供本發明的完整公開並且便於所屬領域的技術人員透徹理解本發明。應注意,附圖的比例並不是精確的,而且為了便於附圖中清楚地描述,有些尺寸,例如寬度、長度、厚度等等經過放大。圖式中將通過類似參考標號表示類似元件。Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It is to be understood that the invention is not to be construed as being limited to the details of the invention. It should be noted that the scale of the drawings is not precise, and that some dimensions, such as width, length, thickness, etc., are exaggerated for ease of clarity in the drawings. Similar elements will be denoted by like reference numerals in the drawings.

本文所使用的如「上」和「下」的空間上相對的術語是參照附圖定義的。因此,應瞭解,「上」與「下」可以互換使用。此外,應理解,當將一個層稱為「在」另一層「上」時,這個層可以直接在另一層上形成或者還可以存在介入層。因此,應理解,當將層稱為「直接在」另一層「上」時,其間不插入介入層。As used herein, spatially relative terms such as "upper" and "lower" are defined with reference to the drawings. Therefore, it should be understood that "upper" and "lower" can be used interchangeably. In addition, it should be understood that when a layer is referred to as being "on" another layer, the layer may be formed directly on the other layer or the intervening layer may be present. Therefore, it should be understood that when a layer is referred to as being "directly on" another layer, the intervening layer is not inserted.

本文所使用的「拉伸模數(tensile modulus)」是根據ASTM D882測量的。As used herein, "tensile modulus" is measured in accordance with ASTM D882.

本文所使用的「剝落強度(peel strength)」是根據JIS2107測量的,並且意味著第一黏著層或第二黏著層與玻璃基板之間的180°剝離強度。As used herein, "peel strength" is measured in accordance with JIS 2107 and means a 180° peel strength between the first adhesive layer or the second adhesive layer and the glass substrate.

本文所使用的在彎曲偏光板時生成的圓形區段的一個點處的術語「曲率半徑」是由圓形區段的對應點處的假想接觸圓的半徑限定的,其中假想接觸圓比任何其他假想圓更接近所述圓形區段。The term "curvature radius" at a point of a circular segment generated when bending a polarizing plate as used herein is defined by the radius of an imaginary contact circle at a corresponding point of a circular segment, wherein the imaginary contact circle is any Other imaginary circles are closer to the circular section.

本文所使用的術語「(甲基)丙烯醯基」是指丙烯醯基和/或甲基丙烯醯基。The term "(meth)acryloyl) as used herein refers to acryloyl and/or methacrylinyl.

本文所使用的「被取代或未被取代的」中的術語「被取代的」意思是相應官能團中的至少一個氫原子被C1 到C10 烷基、羥基、氨基、C6 到C10 芳基、鹵素原子、氰基、C3 到C10 環烷基或C7 到C10 芳烷基取代。The term "substituted" as used herein in the "substituted or unsubstituted" means that at least one hydrogen atom in the corresponding functional group is C 1 to C 10 alkyl, hydroxy, amino, C 6 to C 10 aryl. a group, a halogen atom, a cyano group, a C 3 to C 10 cycloalkyl group or a C 7 to C 10 aralkyl group.

下文中,將參考圖1詳細地描述根據本發明的一個實施例的偏光板。圖1是根據本發明的一個實施例的偏光板的橫截面圖。Hereinafter, a polarizing plate according to an embodiment of the present invention will be described in detail with reference to FIG. 1. 1 is a cross-sectional view of a polarizing plate in accordance with an embodiment of the present invention.

參看圖1,根據本發明的一個實施例的偏光板100可以包含偏光鏡110、保護層120和第一黏著層130。偏光板100可以僅僅在偏光鏡110的一個表面上包含保護層120。由於偏光板100包含第一黏著層130,所以偏光板100可以在斷裂時或在再加工時的惡劣條件下保持耐久性,可以在高溫和/或高濕度條件下或在熱衝擊條件下防止偏光鏡110中產生開裂和/或偏光鏡110的變色,並且可以通過減小偏光板100的厚度而幫助減小光學顯示器的厚度。Referring to FIG. 1, a polarizing plate 100 according to an embodiment of the present invention may include a polarizing mirror 110, a protective layer 120, and a first adhesive layer 130. The polarizing plate 100 may include the protective layer 120 only on one surface of the polarizing mirror 110. Since the polarizing plate 100 includes the first adhesive layer 130, the polarizing plate 100 can maintain durability under breakage or under severe conditions during rework, and can prevent polarization under high temperature and/or high humidity conditions or under thermal shock conditions. The cracking and/or discoloration of the polarizer 110 is generated in the mirror 110, and the thickness of the optical display can be reduced by reducing the thickness of the polarizing plate 100.

偏光板100的厚度可以是大約115微米或更小,具體來說大約108微米或更小,更具體來說大約47微米到大約100微米。在這個厚度範圍內,偏光板可以用於光學顯示器,並且可以幫助減小光學顯示器的厚度。偏光板100的透光率在大約380奈米到大約780奈米的波長下可以大約是30%或更大,具體來說大約30%到大約50%,更具體來說大約40%到大約50%。偏光板100的偏光度可以大約是90%或大於90%,具體來說大約95.000%到大約99.990%。在透光率和偏光度的這些範圍內,偏光板可以用於光學顯示器。The thickness of the polarizing plate 100 may be about 115 microns or less, specifically about 108 microns or less, more specifically about 47 microns to about 100 microns. Within this thickness range, the polarizing plate can be used for optical displays and can help reduce the thickness of the optical display. The light transmittance of the polarizing plate 100 may be about 30% or more at a wavelength of about 380 nm to about 780 nm, specifically about 30% to about 50%, more specifically about 40% to about 50. %. The degree of polarization of the polarizing plate 100 may be about 90% or more, specifically about 95.000% to about 99.990%. In these ranges of light transmittance and degree of polarization, a polarizing plate can be used for an optical display.

下文中,將詳細地描述根據這個實施例的偏光鏡110、保護層120和第一黏著層130以及這些元件的製造方法。Hereinafter, the polarizing mirror 110, the protective layer 120, and the first adhesive layer 130 according to this embodiment, and a method of manufacturing these elements will be described in detail.

偏光鏡110安置於保護層120和第一黏著層130之間,並且可以使進入偏光板100的光偏振。The polarizer 110 is disposed between the protective layer 120 and the first adhesive layer 130, and can polarize light entering the polarizing plate 100.

偏光鏡110的與第一黏著層130鄰接的一個表面可以接受電暈處理、電漿處理和底塗劑處理中的至少一項。因此,偏光鏡110和第一黏著層130之間的剝落強度增加,由此防止偏光鏡110和第一黏著層130之間的分離。可以通過本領域中的典型方法執行偏光鏡110的電暈處理、電漿處理或底塗劑處理。One surface of the polarizer 110 adjacent to the first adhesive layer 130 may receive at least one of corona treatment, plasma treatment, and primer treatment. Therefore, the peeling strength between the polarizer 110 and the first adhesive layer 130 is increased, thereby preventing separation between the polarizer 110 and the first adhesive layer 130. The corona treatment, the plasma treatment, or the primer treatment of the polarizer 110 can be performed by a typical method in the art.

偏光鏡110的厚度可以是大約5微米到大約30微米,具體來說大約5微米到大約20微米。在這個厚度範圍內,偏光鏡可以用於偏光板,並且可以實現偏光板的厚度減小。The polarizer 110 can have a thickness of from about 5 microns to about 30 microns, specifically from about 5 microns to about 20 microns. Within this thickness range, a polarizer can be used for the polarizing plate, and the thickness of the polarizing plate can be reduced.

可以使用聚乙烯醇樹脂膜製造偏光鏡110。具體來說,偏光鏡可以是通過將碘和二色性染料中的至少一個吸收到聚乙烯醇樹脂膜而製造的聚乙烯醇偏光鏡,或者通過使聚乙烯醇樹脂膜脫水而製造的多烯類偏光鏡。聚乙烯醇樹脂膜的皂化度可以是大約85莫耳%到大約100莫耳%,具體來說大約98莫耳%到大約100莫耳%。聚乙烯醇樹脂膜的偏光度可以是大約1,000到大約10,000,具體來說大約1,500到大約10,000。在皂化度和偏光度的這些範圍內,可以使用聚乙烯醇樹脂膜製造偏光鏡。偏光鏡110可以通過本領域中已知的典型方法製造。The polarizer 110 can be manufactured using a polyvinyl alcohol resin film. Specifically, the polarizer may be a polyvinyl alcohol polarizer manufactured by absorbing at least one of iodine and a dichroic dye to a polyvinyl alcohol resin film, or a polyene produced by dehydrating a polyvinyl alcohol resin film. Class of polarizers. The degree of saponification of the polyvinyl alcohol resin film may be from about 85 mol% to about 100 mol%, specifically from about 98 mol% to about 100 mol%. The polyvinyl alcohol resin film may have a degree of polarization of from about 1,000 to about 10,000, specifically from about 1,500 to about 10,000. In these ranges of the degree of saponification and the degree of polarization, a polarizing lens can be produced using a polyvinyl alcohol resin film. The polarizer 110 can be fabricated by a typical method known in the art.

可以在偏光鏡110的一個表面上形成保護層120以保護偏光鏡110。保護層120可以是保護膜或保護塗層。The protective layer 120 may be formed on one surface of the polarizer 110 to protect the polarizer 110. The protective layer 120 may be a protective film or a protective coating.

在一個實施例中,可以通過光學透明樹脂形成的保護膜來實現保護層120。具體來說,光學透明樹脂可以包含選自下面當中的至少一種:環狀聚烯烴樹脂(例如無定形環烯烴聚合物(cyclic olefin polymer,COP))、聚酯樹脂(例如聚(甲基)丙烯酸酯樹脂、聚碳酸酯樹脂和聚對苯二甲酸乙二醇酯(polyethylene terephthalate,PET))、纖維素酯樹脂(例如三乙醯纖維素(triacetylcellulose,TAC))、聚醚碸樹脂、聚碸樹脂、聚醯胺樹脂、聚醯亞胺樹脂、非環狀聚烯烴樹脂、聚芳酯樹脂、聚乙烯醇樹脂、聚氯乙烯樹脂和聚偏二乙烯樹脂。在一個實施例中,保護膜可以是由一種聚酯樹脂形成的單層膜。In one embodiment, the protective layer 120 may be implemented by a protective film formed of an optically transparent resin. Specifically, the optically transparent resin may comprise at least one selected from the group consisting of a cyclic polyolefin resin (for example, an amorphous olefin polymer (COP)), a polyester resin (for example, poly(meth)acrylic acid). Ester resin, polycarbonate resin and polyethylene terephthalate (PET), cellulose ester resin (such as triacetyl cellulose (TAC)), polyether oxime resin, polyfluorene Resin, polyamide resin, polyimide resin, acyclic polyolefin resin, polyarylate resin, polyvinyl alcohol resin, polyvinyl chloride resin, and polyvinylidene chloride resin. In one embodiment, the protective film may be a single layer film formed of a polyester resin.

保護膜的厚度可以是大約5微米到大約200微米,具體來說大約10微米到大約150微米,更具體來說大約20微米到大約100微米。在這個厚度範圍內,保護膜可以用於偏光板,並且可以抑制偏光板連同第一黏著層的翹曲。雖然圖1中未示出,但是保護膜可以經由偏光板用的典型黏合劑被黏合到偏光鏡110,典型黏合劑例如是水類黏合劑或光可固化黏合劑。具體來說,水類黏合劑可以是水與例如聚乙烯醇、聚乙烯亞胺和氧化鋯之類的化合物的混合物。光可固化黏合劑可以是包含環氧樹脂和(甲基)丙烯酸酯樹脂中的至少一個的混合物。The thickness of the protective film can be from about 5 microns to about 200 microns, specifically from about 10 microns to about 150 microns, and more specifically from about 20 microns to about 100 microns. Within this thickness range, the protective film can be used for the polarizing plate, and the warpage of the polarizing plate together with the first adhesive layer can be suppressed. Although not shown in FIG. 1, the protective film may be bonded to the polarizing mirror 110 via a typical adhesive for a polarizing plate, such as a water-based adhesive or a photocurable adhesive. Specifically, the aqueous binder may be a mixture of water and a compound such as polyvinyl alcohol, polyethyleneimine, and zirconia. The photocurable adhesive may be a mixture comprising at least one of an epoxy resin and a (meth) acrylate resin.

在另一個實施例中,可以通過保護塗層實現保護層120。保護塗層可以由包含活化能量射線可固化化合物和起始劑的活化能量射線可固化樹脂組成物形成。In another embodiment, the protective layer 120 can be implemented by a protective coating. The protective coating may be formed of an activated energy ray curable resin composition comprising an activated energy ray curable compound and an initiator.

保護塗層的厚度可以是大約5微米到大約200微米,具體來說大約5微米到大約20微米,更具體來說大約4微米到大約10微米。在這個厚度範圍內,保護塗層可以用於偏光板,可以抑制偏光板連同第一黏著層的翹曲,並且可以幫助減小偏光板的厚度。保護塗層可以直接形成於偏光鏡110上。本文所使用的表達「直接形成」的意思是不存在插入於偏光鏡和保護塗層之間的黏著層和/或黏合層。The protective coating may have a thickness of from about 5 microns to about 200 microns, specifically from about 5 microns to about 20 microns, and more specifically from about 4 microns to about 10 microns. Within this thickness range, the protective coating can be used for the polarizing plate, the warpage of the polarizing plate together with the first adhesive layer can be suppressed, and the thickness of the polarizing plate can be reduced. The protective coating can be formed directly on the polarizer 110. As used herein, the expression "directly formed" means that there is no adhesive layer and/or adhesive layer interposed between the polarizer and the protective coating.

在一些實施例中,雖然圖1中未示出,但是保護層120可進一步包含保護層120的上表面上的功能塗層,用以向偏光板提供另外的功能。具體來說,功能塗層可以包含硬塗層、抗反射層、防指紋層、抗靜電層和低反射層中的至少一個,但不限於此。功能塗層的厚度可以是大約1微米到大約100微米,具體來說大約1微米到大約50微米。在這個厚度範圍內,功能塗層可以向偏光板提供另外的功能,而不會影響另一個保護層並且可以用於偏光板。In some embodiments, although not shown in FIG. 1, the protective layer 120 may further include a functional coating on the upper surface of the protective layer 120 to provide additional functionality to the polarizing plate. Specifically, the functional coating layer may include at least one of a hard coat layer, an antireflection layer, an anti-fingerprint layer, an antistatic layer, and a low reflection layer, but is not limited thereto. The thickness of the functional coating can be from about 1 micron to about 100 microns, specifically from about 1 micron to about 50 microns. Within this thickness range, the functional coating can provide additional functionality to the polarizing plate without affecting the other protective layer and can be used for the polarizing plate.

雖然圖1中未示出,但是在通過保護膜實現保護層120的實施例中,偏光板可進一步包含形成於保護層120的下表面上以改進偏光鏡110和保護層120之間的黏合的底塗層。底塗層可以是親水性表面改性層。通過塗布包含形成底塗層用的樹脂的組成物,藉此可以形成底塗層,該樹脂包含親水基團和疏水基團。形成底塗層用的樹脂可以包含聚酯樹脂和聚乙酸乙烯酯樹脂中的至少一個。底塗層的厚度可以是大約1奈米到大約100奈米,具體來說大約1奈米到大約50奈米。在這個厚度層內,底塗層可以改進與偏光鏡的黏著力,同時改善總透光率。Although not shown in FIG. 1, in an embodiment in which the protective layer 120 is implemented by a protective film, the polarizing plate may further include a lower surface formed on the protective layer 120 to improve adhesion between the polarizing mirror 110 and the protective layer 120. Undercoat. The undercoat layer may be a hydrophilic surface modification layer. By coating a composition containing a resin for forming an undercoat layer, an undercoat layer can be formed, which resin contains a hydrophilic group and a hydrophobic group. The resin for forming the undercoat layer may contain at least one of a polyester resin and a polyvinyl acetate resin. The thickness of the undercoat layer may be from about 1 nanometer to about 100 nanometers, specifically from about 1 nanometer to about 50 nanometers. Within this thickness layer, the undercoat layer can improve adhesion to the polarizer while improving overall light transmittance.

第一黏著層130可以形成於偏光鏡110的另一個表面上,使得偏光板100可以通過其黏著到光學顯示器的光學裝置,例如液晶顯示面板、有機發光裝置、透明導電薄膜等等。The first adhesive layer 130 may be formed on the other surface of the polarizer 110 such that the polarizing plate 100 may be adhered to an optical device of the optical display, such as a liquid crystal display panel, an organic light-emitting device, a transparent conductive film, or the like.

第一黏著層130充當在與保護層120相對的一側安置在偏光鏡110上的阻隔層,以保護偏光鏡110免受例如濕氣和氣體之類的外部環境的損害。另外,第一黏著層130可以在斷裂時或再加工時的惡劣條件下保持耐久性,可以在高溫和/或高濕度條件下或在熱衝擊條件下防止偏光鏡110中產生開裂和/或偏光鏡110的變色,並且可以幫助相比於典型的偏光板減小偏光板的厚度。The first adhesive layer 130 serves as a barrier layer disposed on the polarizer 110 on the side opposite to the protective layer 120 to protect the polarizer 110 from the external environment such as moisture and gas. In addition, the first adhesive layer 130 can maintain durability under severe conditions during breakage or rework, and can prevent cracking and/or polarization in the polarizer 110 under high temperature and/or high humidity conditions or under thermal shock conditions. The discoloration of the mirror 110 can help reduce the thickness of the polarizing plate compared to a typical polarizing plate.

第一黏著層130展現出與偏光鏡110的充分黏著力,並且直接形成於偏光鏡110上,由此能實現偏光板的厚度減小。本文所使用的表達「直接形成」的意思是不存在插入於偏光鏡110和第一黏著層130之間的黏著層和/或黏合層。在一些實施例中,為了改進偏光鏡和第一黏著層之間的黏著力,可以對偏光鏡的另一個表面的1微米或更小的厚度進行底塗劑處理、電暈處理和/或電漿處理。The first adhesive layer 130 exhibits sufficient adhesion to the polarizer 110 and is formed directly on the polarizer 110, whereby the thickness of the polarizing plate can be reduced. As used herein, the expression "directly formed" means that there is no adhesive layer and/or adhesive layer interposed between the polarizer 110 and the first adhesive layer 130. In some embodiments, in order to improve the adhesion between the polarizer and the first adhesive layer, a primer treatment, corona treatment, and/or electricity may be applied to a thickness of 1 micron or less of the other surface of the polarizer. Slurry treatment.

第一黏著層130的厚度可以是大約5微米到大約40微米,具體來說大約5微米到大約20微米。在這個厚度範圍內,第一黏著層可以用於光學顯示器,並且可以實現偏光板的厚度的減小。The thickness of the first adhesive layer 130 can be from about 5 microns to about 40 microns, specifically from about 5 microns to about 20 microns. Within this thickness range, the first adhesive layer can be used for an optical display, and a reduction in thickness of the polarizing plate can be achieved.

第一黏著層130可以包含玻璃轉化溫度大約是50℃或更高的黏著性樹脂。因此,第一黏著層130具有高拉伸模數以防外部濕氣穿透,因此可以容易形成,同時改善偏光板的耐久性。另外,如圖2中所示,在偏光板進一步包含第一黏著層130的下表面上的第二黏著層140的結構中,第一黏著層130和第二黏著層140可以通過同時塗布形成。因此,第一黏著層130和第二黏著層140之間的黏著力可以進一步得到改善,並且第一黏著層130和第二黏著層140之間的介面的圓度(roundness)可以最小化,由此進一步改善偏光板的透光率。The first adhesive layer 130 may contain an adhesive resin having a glass transition temperature of about 50 ° C or higher. Therefore, the first adhesive layer 130 has a high tensile modulus to prevent external moisture from penetrating, and thus can be easily formed while improving the durability of the polarizing plate. In addition, as shown in FIG. 2, in the structure in which the polarizing plate further includes the second adhesive layer 140 on the lower surface of the first adhesive layer 130, the first adhesive layer 130 and the second adhesive layer 140 may be formed by simultaneous coating. Therefore, the adhesion between the first adhesive layer 130 and the second adhesive layer 140 can be further improved, and the roundness of the interface between the first adhesive layer 130 and the second adhesive layer 140 can be minimized by This further improves the light transmittance of the polarizing plate.

具體來說,第一黏著層130的拉伸模數可以是大約10兆帕(MPa)到小於大約2,000兆帕,更具體來說大約50兆帕到大約1500兆帕,再更具體來說大約200兆帕到大約1500兆帕。在此範圍內,第一黏著層可以充當相對於偏光鏡的有效屏障。In particular, the tensile modulus of the first adhesive layer 130 can be from about 10 megapascals (MPa) to less than about 2,000 megapascals, more specifically from about 50 megapascals to about 1500 megapascals, and more specifically about 200 MPa to about 1500 MPa. Within this range, the first adhesive layer can act as an effective barrier against the polarizer.

第一黏著層130可以由第一黏著層用的組成物形成,包含玻璃轉化溫度為大約50℃或更高的黏著性樹脂和如下描述的異氰酸酯類固化劑。因此,第一黏著層130具有低霧度以減小偏光板的霧度,可以展現出良好的可繞性,並且可以實現偏光板的良好耐久性。具體來說,第一黏著層130的霧度在大約380奈米到大約780奈米的波長下可以是大約1%或更小,具體來說大約0.1%到大約0.5%,更具體來說大約0.1%到大約0.2%。具體來說,偏光板100的霧度在大約380奈米到大約780奈米的波長下可以是大約1%或更小,具體來說大約0.1%到大約0.5%,更具體來說大約0.1%到大約0.3%。在這個霧度範圍內,第一黏著層可以用於光學顯示器。使用這樣的第一黏著層,偏光板100展現出良好的可繞性,具有大約10毫米或更小的曲率半徑,具體來說大約1毫米到大約5毫米的曲率半徑,因而可以用於可繞式顯示器。The first adhesive layer 130 may be formed of a composition for the first adhesive layer, and includes an adhesive resin having a glass transition temperature of about 50 ° C or higher and an isocyanate curing agent as described below. Therefore, the first adhesive layer 130 has a low haze to reduce the haze of the polarizing plate, can exhibit good windability, and can achieve good durability of the polarizing plate. In particular, the haze of the first adhesive layer 130 may be about 1% or less, specifically about 0.1% to about 0.5%, more specifically about a wavelength of about 380 nm to about 780 nm. 0.1% to about 0.2%. Specifically, the haze of the polarizing plate 100 may be about 1% or less, specifically about 0.1% to about 0.5%, and more specifically about 0.1% at a wavelength of about 380 nm to about 780 nm. To about 0.3%. Within this haze range, the first adhesive layer can be used for an optical display. With such a first adhesive layer, the polarizing plate 100 exhibits good windability, has a radius of curvature of about 10 mm or less, specifically, a radius of curvature of about 1 mm to about 5 mm, and thus can be used for winding Display.

第一黏著層130可以由第一黏著層用的組成物形成,包含玻璃轉化溫度大約50℃或更高的黏著性樹脂和大量如下描述的異氰酸酯類固化劑。因此,第一黏著層130具有高拉伸模數以防止外部濕氣穿透。另外,第一黏著層130可以在沒有可熱固化的起始劑的情況下對於第一黏著層的組成物的熱固化或室溫固化時將拉伸模數保持在上述範圍內,並且可以相對於受到電漿、電暈電暈或電漿處理的偏光鏡110保持黏著強度,由此阻止偏光鏡110和第一黏著層130之間的分離。在一個實施例中,第一黏著層130的剝落強度可以是大約1,000克力/英寸到大約1800克力/英寸。在剝落強度的此範圍內,第一黏著層可以相對於偏光鏡展現出充分的強度,由此防止偏光鏡110和第一黏著層130之間的分離。The first adhesive layer 130 may be formed of a composition for the first adhesive layer, an adhesive resin having a glass transition temperature of about 50 ° C or higher, and a large amount of an isocyanate curing agent as described below. Therefore, the first adhesive layer 130 has a high tensile modulus to prevent external moisture from penetrating. In addition, the first adhesive layer 130 may maintain the tensile modulus within the above range for thermal curing or room temperature curing of the composition of the first adhesive layer without a heat-curable initiator, and may be relatively The polarizer 110 subjected to plasma, corona corona or plasma treatment maintains adhesive strength, thereby preventing separation between the polarizer 110 and the first adhesive layer 130. In one embodiment, the peel strength of the first adhesive layer 130 can be from about 1,000 gram force per inch to about 1800 gram force per inch. Within this range of peel strength, the first adhesive layer can exhibit sufficient strength with respect to the polarizer, thereby preventing separation between the polarizer 110 and the first adhesive layer 130.

第一黏著層130可以通過對第一黏著層用的組成物的熱固化或室溫固化形成。熱固化包含在大約35℃到大約50℃和大約20%相對濕度(relative humidity,RH)到大約60%RH(具體來說大約35℃和大約45%RH)下在大約24小時到大約48小時中使第一黏著層用的組成物退火。室溫固化包含在大約20℃到小於大約35℃和大約20%RH到大約60%RH下在大約24小時到大約48小時中使第一黏著層用的組成物退火。The first adhesive layer 130 may be formed by heat curing or room temperature curing of the composition for the first adhesive layer. Thermal curing comprises from about 35 ° C to about 50 ° C and about 20% relative humidity (RH) to about 60% RH (specifically about 35 ° C and about 45% RH) in about 24 hours to about 48 hours. The composition for the first adhesive layer is annealed. Curing at room temperature comprises annealing the composition for the first adhesive layer from about 20 ° C to less than about 35 ° C and from about 20% RH to about 60% RH over about 24 hours to about 48 hours.

接下來,將詳細地描述第一黏著層用的組成物。Next, the composition for the first adhesive layer will be described in detail.

第一黏著層用的組成物可以包含玻璃轉化溫度為大約50℃或更高的黏著性樹脂(下文中簡稱為「黏著性樹脂」)和異氰酸酯類固化劑。第一黏著層用的組成物不包含可熱固化起始劑。雖然第一黏著層用的組成物不包含可熱固化起始劑,但是所述組成物包含大量異氰酸酯類固化劑,由此實現高拉伸模數和高黏著強度的黏著層。The composition for the first adhesive layer may contain an adhesive resin (hereinafter simply referred to as "adhesive resin") having a glass transition temperature of about 50 ° C or higher and an isocyanate curing agent. The composition for the first adhesive layer does not contain a heat curable initiator. Although the composition for the first adhesive layer does not contain a heat-curable initiator, the composition contains a large amount of an isocyanate-based curing agent, thereby realizing an adhesive layer having a high tensile modulus and a high adhesive strength.

黏著性樹脂可以是通過熱固化和/或室溫固化形成第一黏著層的膠著劑。在玻璃轉化溫度範圍內,黏著性樹脂可以展現出高拉伸模數,由此實現充當阻隔層的黏著層。黏著性樹脂的玻璃轉化溫度可以是大約50℃或更高,更具體來說大約50℃到大約80℃,例如大約50℃到大約70℃,例如大約50℃到大約60℃。The adhesive resin may be an adhesive that forms a first adhesive layer by heat curing and/or room temperature curing. The adhesive resin can exhibit a high tensile modulus in the glass transition temperature range, thereby realizing an adhesive layer serving as a barrier layer. The glass transition temperature of the adhesive resin may be about 50 ° C or higher, more specifically about 50 ° C to about 80 ° C, such as about 50 ° C to about 70 ° C, such as about 50 ° C to about 60 ° C.

黏著性樹脂可以包含(甲基)丙烯酸共聚物,但不限於此。(甲基)丙烯酸共聚物可以包含(甲基)丙烯酸單體混合物的共聚物。The adhesive resin may contain a (meth)acrylic copolymer, but is not limited thereto. The (meth)acrylic copolymer may comprise a copolymer of a mixture of (meth)acrylic monomers.

(甲基)丙烯酸單體混合物可以包含選自下面當中的至少一種:含經取代或未經取代的C1 到C20 烷基的(甲基)丙烯酸單體、含羥基的(甲基)丙烯酸單體、含被取代或未被取代的C3 到C20 環烷基的(甲基)丙烯酸單體、和含被取代或未被取代的C6 到C20 芳族基的(甲基)丙烯酸單體。這些可以單獨使用或以其組合形式使用。The (meth)acrylic monomer mixture may comprise at least one selected from the group consisting of a substituted or unsubstituted C 1 to C 20 alkyl (meth)acrylic monomer, a hydroxyl group-containing (meth)acrylic acid. a monomer, a (meth)acrylic monomer containing a substituted or unsubstituted C 3 to C 20 cycloalkyl group, and a (meth) group containing a substituted or unsubstituted C 6 to C 20 aromatic group Acrylic monomer. These can be used alone or in combination.

含經取代或未經取代的C1 到C20 烷基的(甲基)丙烯酸單體可以包含含C1 到C20 烷基的(甲基)丙烯酸酯,其中C1 到C20 烷基可以被取代或未被取代。例如,含C1 到C20 烷基的(甲基)丙烯酸酯可以包含選自下面當中的至少一種:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯和(甲基)丙烯酸十二酯,但不限於此。The (meth)acrylic monomer having a substituted or unsubstituted C 1 to C 20 alkyl group may comprise a (meth) acrylate having a C 1 to C 20 alkyl group, wherein the C 1 to C 20 alkyl group may be Replaced or unsubstituted. For example, the (meth) acrylate containing a C 1 to C 20 alkyl group may contain at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , n-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, (meth)acrylic acid 2 -ethylhexyl ester, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate and (methyl) ) Dodecyl acrylate, but is not limited thereto.

含被取代或未被取代的C3 到C20 環烷基的(甲基)丙烯酸單體可以包含含C3 到C20 環烷基的(甲基)丙烯酸酯,其中C3 到C20 環烷基可以被取代或未被取代。例如,含C3 到C20 環烷基的(甲基)丙烯酸酯可以包含(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯和(甲基)丙烯酸異冰片酯中的至少一種。The (meth)acrylic monomer containing a substituted or unsubstituted C 3 to C 20 cycloalkyl group may comprise a (meth) acrylate containing a C 3 to C 20 cycloalkyl group, wherein the C 3 to C 20 ring The alkyl group may be substituted or unsubstituted. For example, the (meth) acrylate containing a C 3 to C 20 cycloalkyl group may contain at least one of cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. .

含被取代或未被取代的C6 到C20 芳族基的(甲基)丙烯酸單體可以包含含C6 到C20 芳族基的(甲基)丙烯酸酯,其中C6 到C20 芳族基可以被取代或未被取代。例如,含C6 到C20 芳族基的(甲基)丙烯酸酯可以包含(甲基)丙烯酸苯酯和(甲基)丙烯酸苯甲酯中的至少一種。The (meth)acrylic monomer containing a substituted or unsubstituted C 6 to C 20 aromatic group may comprise a (meth) acrylate containing a C 6 to C 20 aromatic group, wherein C 6 to C 20 aryl A family group can be substituted or unsubstituted. For example, the (meth) acrylate containing a C 6 to C 20 aromatic group may contain at least one of phenyl (meth) acrylate and benzyl (meth) acrylate.

含羥基的(甲基)丙烯酸單體可以包含下面中的至少一種:含有具有羥基的C1 到C20 烷基的(甲基)丙烯酸單體,含有具有羥基的C3 到C20 環烷基的(甲基)丙烯酸單體,和含有具有羥基的C6 到C20 芳族基的(甲基)丙烯酸單體。具體來說,含羥基的(甲基)丙烯酸單體可以包含選自下面當中的至少一種:(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、(甲基)丙烯酸1-氯-2-羥丙酯、二乙二醇單(甲基)丙烯酸、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸4-羥基環戊酯和(甲基)丙烯酸4-羥基環己酯。這些可以單獨使用或以其組合形式使用。The hydroxyl group-containing (meth)acrylic monomer may comprise at least one of the following: a (meth)acrylic monomer containing a C 1 to C 20 alkyl group having a hydroxyl group, and a C 3 to C 20 cycloalkyl group having a hydroxyl group. a (meth)acrylic monomer, and a (meth)acrylic monomer containing a C 6 to C 20 aromatic group having a hydroxyl group. Specifically, the hydroxyl group-containing (meth)acrylic monomer may comprise at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,4-cyclohexane dimethanol mono (meth) acrylate, (methyl) 1-Chloro-2-hydroxypropyl acrylate, diethylene glycol mono(meth)acrylic acid, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-hydroxycyclopentanyl (meth)acrylate And 4-hydroxycyclohexyl (meth)acrylate. These can be used alone or in combination.

(甲基)丙烯酸共聚物可以通過單體混合物的典型聚合來製備。單體混合物的聚合可以通過所屬領域中已知的典型方法執行。例如,(甲基)丙烯酸共聚物可以如下製備:添加起始劑到單體混合物,接著典型地聚合單體混合物,例如,懸浮聚合、乳液聚合、溶液聚合等等。這裏,聚合可以在大約65℃到大約70℃下執行大約6小時到大約8小時。作為起始劑,可使用任何典型起始劑,包含偶氮基類聚合起始劑和/或過氧化氫聚合起始劑,例如過氧化苯甲醯或過氧化乙醯。The (meth)acrylic copolymer can be prepared by typical polymerization of a monomer mixture. The polymerization of the monomer mixture can be carried out by typical methods known in the art. For example, a (meth)acrylic copolymer can be prepared by adding a starter to a monomer mixture, followed by typically polymerizing a monomer mixture, for example, suspension polymerization, emulsion polymerization, solution polymerization, and the like. Here, the polymerization may be carried out at about 65 ° C to about 70 ° C for about 6 hours to about 8 hours. As the initiator, any typical initiator may be used, including an azo-based polymerization initiator and/or a hydrogen peroxide polymerization initiator such as benzamidine peroxide or ruthenium peroxide.

(甲基)丙烯酸共聚物的重均分子量(Mw)可以是大約1,000,000或更小,具體來說大約50,000到大約500,000,大約500,000到大約1,000,000。在此範圍內,包含(甲基)丙烯酸共聚物的組成物在有效期和塗布穩定性方面可以展現出良好的特性。重均分子量可以根據凝膠滲透色譜法用聚苯乙烯標準物測量。The (meth)acrylic copolymer may have a weight average molecular weight (Mw) of about 1,000,000 or less, specifically about 50,000 to about 500,000, about 500,000 to about 1,000,000. Within this range, the composition containing the (meth)acrylic copolymer can exhibit good characteristics in terms of pot life and coating stability. The weight average molecular weight can be measured by gel permeation chromatography using polystyrene standards.

異氰酸酯類固化劑可以通過熱固化黏著性樹脂而形成黏著層,可以提高第一黏著層的拉伸模數,並且可以相對於受到電暈、電漿和/或底塗劑處理的偏光鏡實現黏著強度。The isocyanate curing agent can form an adhesive layer by thermally curing the adhesive resin, can improve the tensile modulus of the first adhesive layer, and can be adhered to a polarizer treated by corona, plasma and/or primer. strength.

異氰酸酯類固化劑的存在量以100重量份黏著性樹脂計可以是大約5重量份到大約50重量份,具體來說大約5重量份到大約30重量份。在此範圍內,異氰酸酯類固化劑連同不含可熱固化起始劑的黏著性樹脂可以實現高拉伸模數和高黏著強度的黏著層。The isocyanate curing agent may be present in an amount of from about 5 parts by weight to about 50 parts by weight, specifically from about 5 parts by weight to about 30 parts by weight, per 100 parts by weight of the adhesive resin. Within this range, an isocyanate curing agent together with an adhesive resin containing no heat-curable initiator can achieve an adhesive layer having a high tensile modulus and a high adhesive strength.

異氰酸酯類固化劑可以包含經過脲基甲酸酯基團改性的聚異氰酸酯固化劑,由此改善第一黏著層的可繞式,減少第一黏著層和偏光板的霧度,並且改善偏光板的耐久性。例如,異氰酸酯類固化劑可以是經過脲基甲酸酯基團改性的脂肪族聚異氰酸酯固化劑。這裏,脂肪族聚異氰酸酯固化劑包含C4 到C20 二異氰酸酯,例如四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、十二亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯,包含2,2,4-三甲基六亞甲基二異氰酸酯等等。經過脲基甲酸酯基團改性的聚異氰酸酯固化劑可以從市售的產品獲得。The isocyanate curing agent may include a polyisocyanate curing agent modified with an allophanate group, thereby improving the wraparound of the first adhesive layer, reducing the haze of the first adhesive layer and the polarizing plate, and improving the polarizing plate. Durability. For example, the isocyanate curing agent may be an aliphatic polyisocyanate curing agent modified with an allophanate group. Here, the aliphatic polyisocyanate curing agent comprises a C 4 to C 20 diisocyanate such as tetramethylene diisocyanate, hexamethylene diisocyanate, dodecyl diisocyanate, trimethyl hexamethylene diisocyanate, Contains 2,2,4-trimethylhexamethylene diisocyanate and the like. A polyisocyanate curing agent modified with an allophanate group can be obtained from a commercially available product.

第一黏著層用的組成物可以是不含溶劑型組成物,或者可進一步包含溶劑以便改善可塗布性、可塗性或可加工性。溶劑可以包含(但不限於)甲基乙基酮、甲基異丁基酮以及丙二醇單甲基醚乙酸酯,但不限於此。The composition for the first adhesive layer may be a solvent-free composition, or may further contain a solvent in order to improve coatability, coatability, or workability. The solvent may include, but is not limited to, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol monomethyl ether acetate, but is not limited thereto.

第一黏著層用的組成物可進一步包含添加劑。添加劑可以為第一黏著層提供額外的功能。具體來說,添加劑可以包含UV吸收劑、反應抑制劑、助黏劑、觸變劑、傳導性賦予劑、顏色調節劑、穩定劑、抗靜電劑、抗氧化劑和調平劑,但不限於此。The composition for the first adhesive layer may further comprise an additive. The additive can provide additional functionality to the first adhesive layer. Specifically, the additive may include, but is not limited to, a UV absorber, a reaction inhibitor, an adhesion promoter, a thixotropic agent, a conductivity imparting agent, a color modifier, a stabilizer, an antistatic agent, an antioxidant, and a leveling agent. .

第一黏著層用的組成物可進一步包含細顆粒,以進一步改善第一黏著層的硬度和機械強度。細顆粒可以包含二氧化矽、氧化鋁、氧化鋯以及三氧化鈦中的至少一種,但不限於此。細顆粒可以部分或全部用環氧基、(甲基)丙烯酸酯基或乙烯基經過表面處理,以便改善相容性。細顆粒可以具有(但不限於)任何形狀和尺寸。具體來說,細顆粒可以包含具有圓形、片狀、非晶形形狀等等的顆粒。細顆粒的平均粒徑(D50)可以是大約1奈米到大約400奈米,具體來說大約8奈米到大約100奈米。在此範圍內,細顆粒可以改善第一黏著層的硬度,而不會對第一黏著層的表面粗糙度和透明度造成不良影響。The composition for the first adhesive layer may further contain fine particles to further improve the hardness and mechanical strength of the first adhesive layer. The fine particles may include at least one of cerium oxide, aluminum oxide, zirconium oxide, and titanium oxide, but are not limited thereto. The fine particles may be partially or completely surface-treated with an epoxy group, a (meth) acrylate group or a vinyl group in order to improve compatibility. Fine particles can have, but are not limited to, any shape and size. Specifically, the fine particles may contain particles having a circular shape, a sheet shape, an amorphous shape, and the like. The average particle size (D50) of the fine particles may be from about 1 nm to about 400 nm, specifically from about 8 nm to about 100 nm. Within this range, the fine particles can improve the hardness of the first adhesive layer without adversely affecting the surface roughness and transparency of the first adhesive layer.

在第一黏著層用的組成物中,細顆粒的存在量以固體含量計可以是大約3重量%到大約30重量%,具體來說大約5重量%到大約20重量%。在此範圍內,細顆粒可以增加第一黏著層的硬度,而不會影響表面粗糙度和透明度。In the composition for the first adhesive layer, the fine particles may be present in an amount of from about 3% by weight to about 30% by weight, specifically from about 5% by weight to about 20% by weight, based on the solid content. Within this range, the fine particles can increase the hardness of the first adhesive layer without affecting the surface roughness and transparency.

第一黏著層用的組成物的黏度在25℃下為大約5厘泊到大約200厘泊,具體來說大約10厘泊到大約150厘泊。在此範圍內,組成物可以容易形成第一黏著層。The composition for the first adhesive layer has a viscosity of from about 5 centipoise to about 200 centipoise at 25 ° C, specifically from about 10 centipoise to about 150 centipoise. Within this range, the composition can easily form the first adhesive layer.

下文中,將參考圖2詳細地描述根據本發明的另一個實施例的偏光板。圖2是根據本發明的另一個實施例的偏光板的橫截面圖。Hereinafter, a polarizing plate according to another embodiment of the present invention will be described in detail with reference to FIG. 2 is a cross-sectional view of a polarizing plate in accordance with another embodiment of the present invention.

參看圖2,根據本發明的另一個實施例的偏光板200可以包含偏光鏡110、保護層120、第一黏著層130和第二黏著層140。根據這個實施例的偏光板200與根據上面的實施例的偏光板基本上相同,區別只是第二黏著層140。下文中,將描述第二黏著層和根據這個實施例的偏光板的製造方法。Referring to FIG. 2, a polarizing plate 200 according to another embodiment of the present invention may include a polarizing mirror 110, a protective layer 120, a first adhesive layer 130, and a second adhesive layer 140. The polarizing plate 200 according to this embodiment is substantially the same as the polarizing plate according to the above embodiment except for the second adhesive layer 140. Hereinafter, a second adhesive layer and a method of manufacturing the polarizing plate according to this embodiment will be described.

第二黏著層140「直接形成」在第一黏著層130的下表面上。使用這種結構,偏光板可以實現厚度的減小。本文所使用的表達「直接形成」的意思是不存在插入於第一黏著層130和第二黏著層140之間的黏著層和/或黏合層。第一黏著層130包含玻璃轉化溫度大約是50℃或更高的黏著性樹脂。因此,第一黏著層130和第二黏著層140可以通過同時塗布形成,並且第一黏著層130和第二黏著層140之間的介面的圓度可以最小化,由此進一步改善偏光板的透光率。下文將更詳細地描述通過「同時塗布」的形成。The second adhesive layer 140 is "directly formed" on the lower surface of the first adhesive layer 130. With this structure, the polarizing plate can achieve a reduction in thickness. As used herein, the expression "directly formed" means that there is no adhesive layer and/or adhesive layer interposed between the first adhesive layer 130 and the second adhesive layer 140. The first adhesive layer 130 contains an adhesive resin having a glass transition temperature of about 50 ° C or higher. Therefore, the first adhesive layer 130 and the second adhesive layer 140 can be formed by simultaneous coating, and the circularity of the interface between the first adhesive layer 130 and the second adhesive layer 140 can be minimized, thereby further improving the transparency of the polarizing plate. Light rate. The formation by "simultaneous coating" will be described in more detail below.

第二黏著層140的拉伸模數低於第一黏著層130,因而提供良好的應力釋放。因此,第二黏著層140可以在斷裂時或在再加工時的惡劣條件下保持耐久性,並且可以便於將偏光板200黏著到液晶顯示面板。另外,第二黏著層140即使在高溫和/或高濕度條件下,也可以相對於通過偏光鏡的收縮或膨脹的偏光鏡的物理變化釋放應力,從而防止偏光鏡中產生開裂,並且可以通過相對於液晶顯示面板改善可濕性來改善耐久性。偏光板200包含黏著層,黏著層由具有不同拉伸模數的第一黏著層130和第二黏著層140構成,由此同時實現偏光板的阻隔層效應、耐久性改善和厚度減小。The second adhesive layer 140 has a lower tensile modulus than the first adhesive layer 130, thus providing good stress relief. Therefore, the second adhesive layer 140 can maintain durability at the time of breakage or under severe conditions at the time of rework, and can facilitate adhesion of the polarizing plate 200 to the liquid crystal display panel. In addition, the second adhesive layer 140 can release stress with respect to physical changes of the polarized mirror that is contracted or expanded by the polarizer even under high temperature and/or high humidity conditions, thereby preventing cracking in the polarizer, and can be relatively The liquid crystal display panel improves wettability to improve durability. The polarizing plate 200 includes an adhesive layer composed of a first adhesive layer 130 and a second adhesive layer 140 having different tensile moduli, thereby simultaneously achieving a barrier layer effect, durability improvement, and thickness reduction of the polarizing plate.

具體來說,第二黏著層140的拉伸模數大約是0.01兆帕到小於大約1兆帕,具體來說大約0.05兆帕到大約0.15兆帕,例如大約0.05兆帕到大約0.1兆帕。在此範圍內,第二黏著層140可以通過偏光鏡的收縮或膨脹相對於偏光鏡的物理變化保持應力釋放。In particular, the second adhesive layer 140 has a tensile modulus of from about 0.01 MPa to less than about 1 MPa, specifically from about 0.05 MPa to about 0.15 MPa, such as from about 0.05 MPa to about 0.1 MPa. Within this range, the second adhesive layer 140 can maintain stress release by physical contraction of the polarizer against shrinkage or expansion of the polarizer.

第二黏著層140的剝落強度低於第一黏著層130。因此,第二黏著層140即使在高溫和/或高濕度條件下,也可以通過偏光鏡的收縮或膨脹來相對於偏光鏡的物理變化釋放應力,從而防止偏光鏡中產生開裂,並且可以通過相對於液晶顯示面板改善可濕性來改善耐久性。具體來說,第二黏著層140的玻璃剝落強度可以是大約100克力/英寸到大約1,000克力/英寸,更具體來說大約200克力/英寸到大約800克力/英寸,又更具體來說大約200克力/英寸到大約700克力/英寸。The peeling strength of the second adhesive layer 140 is lower than that of the first adhesive layer 130. Therefore, the second adhesive layer 140 can release stress with respect to the physical change of the polarizer by contraction or expansion of the polarizer even under high temperature and/or high humidity conditions, thereby preventing cracking in the polarizer, and can be relatively The liquid crystal display panel improves wettability to improve durability. In particular, the second adhesive layer 140 may have a glass peel strength of from about 100 gram force per inch to about 1,000 gram force per inch, more specifically from about 200 gram force per inch to about 800 gram force per inch, and more specifically For about 200 grams force per inch to about 700 grams force per inch.

第二黏著層140的厚度大於第一黏著層130,由此在偏光鏡收縮或膨脹時提供應力釋放效應,同時改善玻璃剝落強度。第二黏著層140的厚度可以是大約15微米到大約30微米,具體來說大約15微米到大約25微米。在這個厚度範圍內,第二黏著層140可以改善偏光板的可加工性和耐久性。The thickness of the second adhesive layer 140 is greater than that of the first adhesive layer 130, thereby providing a stress release effect when the polarizer contracts or expands, while improving the glass peeling strength. The thickness of the second adhesive layer 140 can be from about 15 microns to about 30 microns, specifically from about 15 microns to about 25 microns. Within this thickness range, the second adhesive layer 140 can improve the processability and durability of the polarizing plate.

第一黏著層130和第二黏著層140的總厚度的範圍可以是從大約20微米到大約40微米,具體來說大約25微米到大約40微米。在這個厚度範圍內,偏光板可以展現出良好的可切割性。The total thickness of the first adhesive layer 130 and the second adhesive layer 140 may range from about 20 microns to about 40 microns, specifically from about 25 microns to about 40 microns. Within this thickness range, the polarizing plate can exhibit good cuttability.

第二黏著層140可以由第二黏著層用的組成物形成。下文中,將描述第二黏著層用的組成物。The second adhesive layer 140 may be formed of a composition for the second adhesive layer. Hereinafter, the composition for the second adhesive layer will be described.

第二黏著層用的組成物包含(甲基)丙烯酸共聚物和固化劑。The composition for the second adhesive layer contains a (meth)acrylic copolymer and a curing agent.

(甲基)丙烯酸共聚物的重均分子量可以是大約1,000,000或更小,具體來說大約200,000到大約1,000,000,(甲基)丙烯酸共聚物的玻璃轉化溫度可以是大約-50℃到大約-30℃,具體來說大約-50℃到大約-40℃。在這些範圍內,包含(甲基)丙烯酸共聚物的組成物可以在偏光鏡收縮或膨脹時保持應力釋放。The (meth)acrylic copolymer may have a weight average molecular weight of about 1,000,000 or less, specifically about 200,000 to about 1,000,000, and the (meth)acrylic copolymer may have a glass transition temperature of about -50 ° C to about -30 ° C. Specifically, it is about -50 ° C to about -40 ° C. Within these ranges, the composition comprising the (meth)acrylic copolymer can maintain stress release when the polarizer shrinks or expands.

(甲基)丙烯酸共聚物可以包含一種包含含烷基的(甲基)丙烯酸單體和含羥基的(甲基)丙烯酸單體的單體混合物的(甲基)丙烯酸共聚物。The (meth)acrylic copolymer may comprise a (meth)acrylic copolymer comprising a monomer mixture of an alkyl-containing (meth)acrylic monomer and a hydroxyl-containing (meth)acrylic monomer.

含烷基的(甲基)丙烯酸單體可以包含含未被取代或被取代的C1 到C20 烷基的(甲基)丙烯酸酯。具體來說,含烷基的(甲基)丙烯酸單體可以包含選自(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸戊酯和(甲基)丙烯酸2-乙基己酯當中的至少一種。這些可以單獨使用或以其組合形式使用。The alkyl group-containing (meth)acrylic monomer may contain a (meth) acrylate containing an unsubstituted or substituted C 1 to C 20 alkyl group. Specifically, the alkyl group-containing (meth)acrylic monomer may comprise ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, or (meth)acrylate At least one of an ester and 2-ethylhexyl (meth)acrylate. These can be used alone or in combination.

含羥基的(甲基)丙烯酸單體可以包含含有具有至少一個羥基的C1 到C20 烷基的(甲基)丙烯酸酯。具體來說,含羥基的(甲基)丙烯酸單體可以包含(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-羥丙酯和(甲基)丙烯酸4-羥丁酯中的至少一種。這些可以單獨使用或以其組合形式使用。The hydroxyl group-containing (meth)acrylic monomer may comprise a (meth) acrylate containing a C 1 to C 20 alkyl group having at least one hydroxyl group. Specifically, the hydroxyl group-containing (meth)acrylic monomer may comprise 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. At least one. These can be used alone or in combination.

單體混合物可以包含以固體含量計的大約70重量份到大約99重量份的含烷基的(甲基)丙烯酸單體,具體來說大約75重量份到大約90重量份的含烷基的(甲基)丙烯酸單體,大約1重量份到大約30重量份的含羥基的(甲基)丙烯酸單體,具體來說大約10重量份到大約25重量份的含羥基的(甲基)丙烯酸單體。在此範圍內,包含所述單體混合物的組成物可以相對於第一黏著層和黏附體(例如液晶面板的玻璃板)展現出高黏著力。「以固體含量計」這種表達的意思是單體混合物的除了溶劑之外的其餘組分的總重量。The monomer mixture may comprise from about 70 parts by weight to about 99 parts by weight, based on the solids content, of the alkyl group-containing (meth)acrylic monomer, specifically from about 75 parts by weight to about 90 parts by weight of the alkyl group-containing ( a methyl methacrylate monomer, from about 1 part by weight to about 30 parts by weight of a hydroxyl group-containing (meth)acrylic monomer, specifically from about 10 parts by weight to about 25 parts by weight of a hydroxyl group-containing (meth)acrylic acid monomer body. Within this range, the composition comprising the monomer mixture can exhibit high adhesion with respect to the first adhesive layer and the adherend (for example, a glass plate of a liquid crystal panel). By "solids content" this expression means the total weight of the remaining components of the monomer mixture other than the solvent.

(甲基)丙烯酸共聚物可以通過典型的方法來製備。具體來說,(甲基)丙烯酸共聚物可以通過如下方式製備:將起始劑添加到單體混合物,然後在大約50℃到大約100℃下反應。起始劑可以是2,2'-偶氮二異丁腈(azobisisobutyronitrile,AIBN),但不限於此。起始劑的存在量以單體混合物的100重量份計可以是大約0.01重量份到大約1重量份。在此範圍內,可以用高產量生產(甲基)丙烯酸共聚物。The (meth)acrylic copolymer can be produced by a typical method. Specifically, the (meth)acrylic copolymer can be prepared by adding an initiator to the monomer mixture and then reacting at about 50 ° C to about 100 ° C. The initiator may be 2,2'-azobisisobutyronitrile (AIBN), but is not limited thereto. The initiator may be present in an amount of from about 0.01 parts by weight to about 1 part by weight based on 100 parts by weight of the monomer mixture. Within this range, a (meth)acrylic copolymer can be produced in a high yield.

(甲基)丙烯酸共聚物可進一步包含典型的含脂環基的(甲基)丙烯酸單體、含芳族基的(甲基)丙烯酸單體、和含羧酸基的單體以及含烷基的(甲基)丙烯酸單體和含羥基的(甲基)丙烯酸單體中的至少一種。The (meth)acrylic copolymer may further comprise a typical alicyclic group-containing (meth)acrylic monomer, an aromatic group-containing (meth)acrylic monomer, and a carboxylic acid group-containing monomer and an alkyl group-containing At least one of a (meth)acrylic monomer and a hydroxyl group-containing (meth)acrylic monomer.

固化劑用以使(甲基)丙烯酸共聚物固化,並且可以包含典型的異氰酸酯固化劑、環氧樹脂固化劑、亞胺固化劑、金屬螯合物固化劑或碳化二亞胺固化劑。具體來說,固化劑可以包含選自六亞甲基二異氰酸酯、甲苯二異氰酸酯(toluene diisocyanate,TDI)、二甲苯二異氰酸酯、異佛爾酮二異氰酸酯、萘二異氰酸酯和用三羥甲基丙烷改性的甲苯二異氰酸酯的加成物當中的至少一種。固化劑的存在量以100重量份(甲基)丙烯酸共聚物計可以是大約0.1重量份到大約1重量份,具體來說大約0.1重量份到大約0.5重量份。在此範圍內,組成物可以充分交聯,由此展現出黏著效應。The curing agent is used to cure the (meth)acrylic copolymer, and may include a typical isocyanate curing agent, an epoxy resin curing agent, an imine curing agent, a metal chelate curing agent, or a carbodiimide curing agent. Specifically, the curing agent may comprise a compound selected from the group consisting of hexamethylene diisocyanate, toluene diisocyanate (TDI), xylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, and trimethylolpropane. At least one of the adducts of the toluene diisocyanate. The curing agent may be present in an amount of from about 0.1 part by weight to about 1 part by weight, specifically from about 0.1 part by weight to about 0.5 part by weight, per 100 parts by weight of the (meth)acrylic copolymer. Within this range, the composition can be sufficiently crosslinked, thereby exhibiting an adhesive effect.

第二黏著層用的黏著組成物可進一步包含矽烷偶合劑和交聯催化劑中的至少一種。The adhesive composition for the second adhesive layer may further contain at least one of a decane coupling agent and a crosslinking catalyst.

矽烷偶合劑可以增加黏著組成物形成的第二黏著層的黏著強度。矽烷偶合劑可以是含環氧基的矽烷偶合劑,例如縮水甘油氧基丙基三甲氧基矽烷、縮水甘油氧基丙基甲基二甲氧基矽烷等等。矽烷偶合劑的存在量以100重量份(甲基)丙烯酸共聚物計可以是大約0.1重量份到大約5重量份。在此範圍內,矽烷偶合劑可以增加黏著組成物的黏著強度。交聯催化劑可以改善黏著組成物形成的黏著層的交聯度。交聯催化劑可以包含金屬或含金屬化合物中的至少一種。具體來說,交聯催化劑可以包含含錫化合物、含鋅化合物、鈦化合物和鉍化合物中的至少一種。更具體來說,交聯催化劑可以包含二月桂酸二丁基錫和二馬來酸錫中的至少一種。交聯催化劑的存在量以100重量份(甲基)丙烯酸共聚物計可以是大約0.01重量份到大約1.5重量份。在此範圍內,交聯催化劑可以增加黏著組成物的交聯度,同時抑制濕氣滲透。The decane coupling agent can increase the adhesion strength of the second adhesive layer formed by the adhesive composition. The decane coupling agent may be an epoxy group-containing decane coupling agent such as glycidoxypropyltrimethoxydecane, glycidoxypropylmethyldimethoxydecane, and the like. The decane coupling agent may be present in an amount of from about 0.1 part by weight to about 5 parts by weight per 100 parts by weight of the (meth)acrylic copolymer. Within this range, the decane coupling agent can increase the adhesion strength of the adhesive composition. The crosslinking catalyst can improve the degree of crosslinking of the adhesive layer formed by the adhesive composition. The crosslinking catalyst may comprise at least one of a metal or a metal-containing compound. Specifically, the crosslinking catalyst may include at least one of a tin-containing compound, a zinc-containing compound, a titanium compound, and a cerium compound. More specifically, the crosslinking catalyst may include at least one of dibutyltin dilaurate and tin dimaleate. The crosslinking catalyst may be present in an amount of from about 0.01 part by weight to about 1.5 parts by weight based on 100 parts by weight of the (meth)acrylic copolymer. Within this range, the crosslinking catalyst can increase the degree of crosslinking of the adhesive composition while suppressing moisture permeation.

下文中,將描述根據本發明的一個實施例的一種製造偏光板的方法。Hereinafter, a method of manufacturing a polarizing plate according to an embodiment of the present invention will be described.

根據本發明的一個實施例的製造偏光板的方法可以包含:層合偏光鏡,所述偏光鏡的至少一個表面受到電暈處理、電漿處理和底塗劑處理中的至少一種處理,並且所述偏光鏡包含形成於它的另一個表面上的保護層以及第一黏著層用的薄片;以及使所述第一黏著層用的所述薄片固化。A method of manufacturing a polarizing plate according to an embodiment of the present invention may include: laminating a polarizer, at least one surface of which is subjected to at least one of a corona treatment, a plasma treatment, and a primer treatment, and The polarizer includes a protective layer formed on the other surface thereof and a sheet for the first adhesive layer; and the sheet for the first adhesive layer is cured.

例如,偏光鏡的一個表面或薄膜型保護層的有待附接到偏光鏡上的一個表面可以接受電暈處理、電漿處理和底塗劑處理中的至少一種處理。可以在偏光鏡或保護層的一個表面上施加水類黏合劑或光可固化黏合劑。另外,偏光鏡的另一個表面可以接受電暈處理、電漿處理和底塗劑處理中的至少一種處理,以便改進偏光鏡和第一黏著層之間的剝落強度。具體來說,電暈處理和電漿處理啟動形成偏光鏡的聚乙烯醇薄膜中的羥基,使之與異氰酸酯類固化劑反應,由此改善第一黏著層與偏光鏡的剝落強度。電暈處理可以在大約50劑量到大約150劑量下執行。在此範圍內,電暈處理可以容易保證黏著強度,而又不會影響偏光鏡的偏光效應。可以在真空下或大氣壓下供應氮氣或氬氣以使用放電產生電漿,藉此對偏光鏡的表面執行電漿處理。可以將底塗劑溶液沉積到保護層(保護膜)或第一黏著層的一個表面上,藉此執行底塗劑處理。底塗劑可以包含聚酯樹脂、聚乙酸乙烯酯樹脂和聚胺酯樹脂中的至少一種。For example, one surface of the polarizer or one surface of the film-type protective layer to be attached to the polarizer may be subjected to at least one of corona treatment, plasma treatment, and primer treatment. A water-based adhesive or a photocurable adhesive may be applied to one surface of the polarizer or the protective layer. In addition, the other surface of the polarizer may be subjected to at least one of corona treatment, plasma treatment, and primer treatment to improve the peel strength between the polarizer and the first adhesive layer. Specifically, the corona treatment and the plasma treatment start the hydroxyl groups in the polyvinyl alcohol film forming the polarizer to react with the isocyanate curing agent, thereby improving the peeling strength of the first adhesive layer and the polarizer. The corona treatment can be performed at a dose of from about 50 doses to about 150 doses. Within this range, corona treatment can easily ensure the adhesion strength without affecting the polarizing effect of the polarizer. Nitrogen or argon may be supplied under vacuum or atmospheric pressure to generate a plasma using the discharge, thereby performing a plasma treatment on the surface of the polarizer. The primer solution may be deposited on the protective layer (protective film) or one surface of the first adhesive layer, whereby the primer treatment is performed. The primer may include at least one of a polyester resin, a polyvinyl acetate resin, and a polyurethane resin.

通過將第一黏著層用的組成物塗布到離型薄膜上、接著執行乾燥,藉此可以製造第一黏著層用的薄片。乾燥可以在大約30℃到大約150℃下執行大約1分鐘到大約2小時。The sheet for the first adhesive layer can be produced by applying the composition for the first adhesive layer onto the release film and then performing drying. Drying can be carried out at about 30 ° C to about 150 ° C for about 1 minute to about 2 hours.

此後,將偏光鏡的一個表面與第一黏著層用的薄片層合,接著執行固化。如上所述,固化可以包含熱固化和室溫固化。Thereafter, one surface of the polarizer is laminated with the sheet for the first adhesive layer, followed by curing. As noted above, curing can include thermal curing and room temperature curing.

應理解,在將第一黏著層用的薄片與偏光鏡的接受電暈處理、電漿處理和底塗劑處理中的至少一種處理的一個表面層合接著固化之後,可以在偏光鏡的另一個表面上形成保護膜。It should be understood that after laminating a sheet for the first adhesive layer with one surface of the polarizer for at least one of corona treatment, plasma treatment, and primer treatment, it may be another one of the polarizers. A protective film is formed on the surface.

下文中,將描述根據本發明的另一個實施例的製造偏光板的方法。Hereinafter, a method of manufacturing a polarizing plate according to another embodiment of the present invention will be described.

根據本發明的另一個實施例的製造偏光板的方法可以包含:通過同時塗布第二黏著層用的組成物和第一黏著層用的組成物、隨後執行乾燥,藉此形成包含第二黏著層用的薄片和形成在其上的第一黏著層用的薄片的堆疊結構;將第一黏著層用的薄片與偏光鏡層合,隨後固化第二黏著層用的薄片和第一黏著層用的薄片。A method of manufacturing a polarizing plate according to another embodiment of the present invention may include: forming a second adhesive layer by simultaneously coating a composition for a second adhesive layer and a composition for a first adhesive layer, followed by performing drying a stacked structure of a sheet for use and a first adhesive layer formed thereon; laminating a sheet for the first adhesive layer with a polarizer, and subsequently curing the sheet for the second adhesive layer and the first adhesive layer Sheet.

下文中,將參看圖3描述根據本發明的另一個實施例的製造偏光板的方法。Hereinafter, a method of manufacturing a polarizing plate according to another embodiment of the present invention will be described with reference to FIG.

參看圖3,將第二黏著層用的組成物14和第一黏著層用的組成物13同時塗布到離型薄膜10上。本文所使用的術語「同時塗布」是指這樣一種處理:將第一黏著層用的組成物直接塗布到第二黏著層用的組成物上,在塗布第二黏著層用的組成物之後並未使第二黏著層用的組成物乾燥。塗布可以通過任何方法執行,但是不限於任何方法。例如,塗布可以通過棒塗、模塗等等執行。可以在含有第二黏著層用的組成物的塗層接觸含有第一黏著層用的組成物的塗布機的狀態下執行同時塗布。以此方式,同時塗布第二黏著層用的組成物和第一黏著層用的組成物,由此降低製造成本,同時改善第一黏著層和第二黏著層之間的黏著力。Referring to Fig. 3, the composition 14 for the second adhesive layer and the composition 13 for the first adhesive layer are simultaneously applied onto the release film 10. The term "simultaneous coating" as used herein refers to a treatment in which the composition for the first adhesive layer is directly applied to the composition for the second adhesive layer, and after the composition for the second adhesive layer is applied, The composition for the second adhesive layer is dried. Coating can be performed by any method, but is not limited to any method. For example, the coating can be performed by bar coating, die coating, or the like. Simultaneous coating can be performed in a state where the coating layer containing the composition for the second adhesive layer contacts the coater containing the composition for the first adhesive layer. In this manner, the composition for the second adhesive layer and the composition for the first adhesive layer are simultaneously coated, thereby reducing the manufacturing cost while improving the adhesion between the first adhesive layer and the second adhesive layer.

雖然圖3中未示出,但是可以例如在真空箱中在真空下執行塗布。另外,雖然圖3中未示出,但是離型薄膜在輥上移動,由此改善可加工性。Although not shown in FIG. 3, the coating can be performed under vacuum, for example, in a vacuum box. Further, although not shown in Fig. 3, the release film moves on the roller, thereby improving workability.

此後,將同時塗布到離型薄膜10上的第二黏著層用的組成物14和第一黏著層用的組成物13乾燥,以形成堆疊結構,其中第一黏著層用的薄片13'和第二黏著層用的薄片14'形成於離型薄膜10上。在30℃到150℃下執行1分鐘到2小時的乾燥。此後,將上面形成有保護層120的偏光鏡110與第一黏著層用的薄片13'組合並且使之乾燥,由此提供如圖2中所示的偏光板。Thereafter, the composition 14 for the second adhesive layer and the composition 13 for the first adhesive layer simultaneously coated on the release film 10 are dried to form a stacked structure, wherein the first adhesive layer 13' and the first adhesive layer A sheet 14' for the two adhesive layers is formed on the release film 10. Drying is carried out at 30 ° C to 150 ° C for 1 minute to 2 hours. Thereafter, the polarizing mirror 110 on which the protective layer 120 is formed is combined with the sheet 13' for the first adhesive layer and dried, thereby providing a polarizing plate as shown in FIG. 2.

雖然圖3中未示出,但是偏光鏡可以先接受電暈處理、電漿處理和底塗劑處理中的至少一項處理,然後與第一黏著層用的薄片層合。電暈處理、電漿處理或底塗劑處理可以改善偏光鏡與第一黏著層用的薄片之間的黏著力。如上所述,固化可以包含熱固化和室溫固化中的至少一種。Although not shown in FIG. 3, the polarizer may be subjected to at least one of corona treatment, plasma treatment, and primer treatment, and then laminated with the sheet for the first adhesive layer. Corona treatment, plasma treatment or primer treatment can improve the adhesion between the polarizer and the sheet for the first adhesive layer. As described above, the curing may include at least one of heat curing and room temperature curing.

根據本發明的另一實施例的製造偏光板的方法可以包含:塗布和乾燥第二黏著層用的組成物以製備第二黏著層用的薄片;塗布和乾燥在第二黏著層用的薄片上的第一黏著層用的組成物以形成堆疊結構,在所述堆疊結構中形成第一黏著層用的薄片和第二黏著層用的薄片;以及將第一黏著層用的薄片與偏光鏡層合,接著執行乾燥。根據這個實施例的方法與根據所述一個實施例的方法基本上相同,區別在於第一黏著層用的組成物在形成第二黏著層用的薄片之後被塗布和乾燥。A method of manufacturing a polarizing plate according to another embodiment of the present invention may include: coating and drying a composition for a second adhesive layer to prepare a sheet for a second adhesive layer; coating and drying on a sheet for a second adhesive layer a composition for the first adhesive layer to form a stacked structure in which a sheet for the first adhesive layer and a sheet for the second adhesive layer are formed; and a sheet for the first adhesive layer and the polarizer layer Then, it is dried. The method according to this embodiment is substantially the same as the method according to the one embodiment, except that the composition for the first adhesive layer is coated and dried after forming the sheet for the second adhesive layer.

根據一個實施例的一種用於光學顯示器的裝置可以包含根據本發明的實施例的偏光板,以及形成於偏光板的上表面上並且包含量子點的薄膜。所述薄膜可以改善彩色再現和可視度。An apparatus for an optical display according to an embodiment may include a polarizing plate according to an embodiment of the present invention, and a film formed on an upper surface of the polarizing plate and containing quantum dots. The film can improve color reproduction and visibility.

根據一個實施例的光學顯示器可以包含根據本發明的實施例的偏光板。所述光學顯示器可以包含液晶顯示器,有機發光顯示器和可繞式有機發光顯示器,但不限於此。所述光學顯示器可以包含可視度改善後的薄膜,所述可視度改善後的薄膜包含量子點以改善彩色再現和可視度。An optical display according to an embodiment may include a polarizing plate according to an embodiment of the present invention. The optical display may include a liquid crystal display, an organic light emitting display, and a wrapable organic light emitting display, but is not limited thereto. The optical display can include a film with improved visibility that includes quantum dots to improve color reproduction and visibility.

在下文中,將參考一些實例更詳細描述本發明。然而,應瞭解,這些實例只是為了說明而提供並且不應以任何方式解釋為限制本發明。Hereinafter, the present invention will be described in more detail with reference to some examples. However, it is to be understood that the examples are provided for illustration only and are not to be construed as limiting the invention in any way.

實例和比較例中所用組分的詳情如下。Details of the components used in the examples and comparative examples are as follows.

(A)第一黏著層用的組成物(A) composition for the first adhesive layer

(A1)黏著性樹脂:1335B(玻璃轉化溫度:50℃,三和有限公司(Samhwa Co., Ltd.))(A1) Adhesive resin: 1335B (glass transition temperature: 50 ° C, Samhwa Co., Ltd.)

(A2)黏著性樹脂:1335F(玻璃轉化溫度:30℃,三和有限公司)(A2) Adhesive resin: 1335F (glass transition temperature: 30 ° C, Sanhe Co., Ltd.)

(A3)異氰酸酯類固化劑:AE700-100(經過脲基甲酸酯基團改性的六亞甲基二異氰酸酯,旭化成化學公司(Asahi Kasei Chemical Co.))(A3) Isocyanate curing agent: AE700-100 (hexamethylene diisocyanate modified with allophanate groups, Asahi Kasei Chemical Co.)

(A4)異氰酸酯類固化劑:TDI(甲苯二異氰酸酯)類固化劑(Coronate  L,不含脲基甲酸酯基團,日本胺基甲酸酯有限公司(Japan Urethane Co., Ltd.))(A4) Isocyanate curing agent: TDI (toluene diisocyanate) type curing agent (Coronate L, no allophanate group, Japan Urethane Co., Ltd.)

(B)第二黏著層用的組成物(B) composition for the second adhesive layer

(B1)(甲基)丙烯酸共聚物:80重量%的丙烯酸丁酯和20重量%的2-羥基乙基丙烯酸酯的(甲基)丙烯酸共聚物(重均分子量:1,000,000,玻璃轉化溫度:-50℃)(B1) (meth)acrylic copolymer: 80% by weight of butyl acrylate and 20% by weight of (meth)acrylic copolymer of 2-hydroxyethyl acrylate (weight average molecular weight: 1,000,000, glass transition temperature: - 50 ° C)

(B2)固化劑:Coronate L(日本胺基甲酸酯有限公司)(B2) Curing agent: Coronate L (Japan Amino Formate Co., Ltd.)

(B3)矽烷偶合劑:KBM403(信越化學有限公司(Shin-Etsu Chemical Co., Ltd.))(B3) decane coupling agent: KBM403 (Shin-Etsu Chemical Co., Ltd.)

(C)保護膜:常用TAC薄膜(KC4DR -1,厚度:40微米,柯尼卡有限公司(Konica Co., Ltd.))(C) Protective film: Common TAC film (KC4DR -1, thickness: 40 μm, Konica Co., Ltd.)

(D)水類黏合劑:通過混合以下物質製備:3.5重量份的聚乙烯醇粉末(Z-320,日本合成工業(Nippon Synthetic IND)),1重量份的聚乙二亞胺(日本觸媒有限公司(Nippon Shokubai Co., Ltd.)),和0.1重量份的氧化鋯(日本稀有元素有限公司(Nippon Rare Element Co., Ltd.)),以及100重量份的水。(D) Water-based binder: Prepared by mixing: 3.5 parts by weight of polyvinyl alcohol powder (Z-320, Nippon Synthetic IND), 1 part by weight of polyethylenediamine (Japanese catalyst) Nippon Shokubai Co., Ltd., and 0.1 part by weight of zirconia (Nippon Rare Element Co., Ltd.), and 100 parts by weight of water.

實例1Example 1

第一黏著層用的組成物通過混合100重量份的(A1)黏著性樹脂與30重量份的(A3)異氰酸酯類固化劑製備。第二黏著層用的組成物通過混合100重量份的(B1)(甲基)丙烯酸共聚物、0.2重量份的(B2)固化劑和0.1重量份的(B3)矽烷偶合劑製備。第二黏著層用的組成物和第一黏著層用的組成物被同時塗布到聚對苯二甲酸乙二醇酯(polyethylene terephthalate,PET)離型薄膜上,並且在90℃下乾燥30分鐘,由此製備堆疊薄片,在所述堆疊薄片中,第二黏著層用的薄片和第一黏著層用的薄片依次堆疊在PET離型薄膜上。The composition for the first adhesive layer was prepared by mixing 100 parts by weight of (A1) adhesive resin with 30 parts by weight of (A3) isocyanate-based curing agent. The composition for the second adhesive layer was prepared by mixing 100 parts by weight of (B1) (meth)acrylic acid copolymer, 0.2 part by weight of (B2) curing agent, and 0.1 part by weight of (B3) decane coupling agent. The composition for the second adhesive layer and the composition for the first adhesive layer are simultaneously coated on a polyethylene terephthalate (PET) release film, and dried at 90 ° C for 30 minutes. Thus, a stacked sheet in which the sheet for the second adhesive layer and the sheet for the first adhesive layer were sequentially stacked on the PET release film were prepared.

聚乙烯醇薄膜(皂化度:99.5莫耳%,偏光度:2,000,厚度:80微米,可樂麗有限公司(Kuraray Co., Ltd.))在0.3%碘溶液中染色。接著,在一個軸向方向上將薄膜拉伸到5.0的伸長率。在3%硼酸溶液和2%碘化鉀溶液中浸漬拉伸後的聚乙烯醇以執行顏色校正。此後,將薄膜在50℃下乾燥4分鐘,由此製造偏光鏡(厚度:12微米)。A polyvinyl alcohol film (saponification degree: 99.5 mol%, polarizing degree: 2,000, thickness: 80 μm, Kuraray Co., Ltd.) was dyed in a 0.3% iodine solution. Next, the film was stretched to an elongation of 5.0 in one axial direction. The stretched polyvinyl alcohol was immersed in a 3% boric acid solution and a 2% potassium iodide solution to perform color correction. Thereafter, the film was dried at 50 ° C for 4 minutes, thereby producing a polarizing mirror (thickness: 12 μm).

所述(C)保護膜使用(D)水類黏合劑被黏合到偏光鏡的一個表面,並且偏光鏡的另一個表面接受50劑量的電暈處理。堆疊薄片的第一黏著層用的薄片與接受電暈處理的偏光鏡的表面層合,並且在35℃和45%RH下接受固化,隨後移除PET薄膜,由此製造偏光板。The (C) protective film was bonded to one surface of the polarizer using (D) an aqueous binder, and the other surface of the polarizer was subjected to a 50-dose corona treatment. The sheet for the first adhesive layer of the stacked sheets was laminated with the surface of the corona-treated polarizer, and cured at 35 ° C and 45% RH, followed by removal of the PET film, thereby manufacturing a polarizing plate.

實例2到實例5Example 2 to Example 5

偏光板的製造方式與實例1中相同,區別是如表1所列改變了第一黏著層用的組成物的組分量。The polarizing plate was produced in the same manner as in Example 1 except that the composition amount of the composition for the first adhesive layer was changed as listed in Table 1.

實例6Example 6

偏光板的製造方式與實例3中相同,區別是如表1所列改變了第一黏著層和第二黏著層中的每一個黏著層的厚度。The polarizing plate was manufactured in the same manner as in Example 3 except that the thickness of each of the first adhesive layer and the second adhesive layer was changed as listed in Table 1.

實例7Example 7

偏光板的製造方式與實例1中相同,區別是如表1中所列改變了偏光鏡、第一黏著層和第二黏著層中的每一個的厚度。The polarizing plate was manufactured in the same manner as in Example 1 except that the thickness of each of the polarizing mirror, the first adhesive layer, and the second adhesive layer was changed as listed in Table 1.

比較例1Comparative example 1

第一黏著層用的組成物通過混合100重量份的(A2)黏著性樹脂與30重量份的(A3)異氰酸酯類固化劑製備。使用第一黏著層用的製備組成物以與實例1中相同的方式製造偏光板。The composition for the first adhesive layer was prepared by mixing 100 parts by weight of (A2) adhesive resin with 30 parts by weight of (A3) isocyanate-based curing agent. A polarizing plate was produced in the same manner as in Example 1 using the preparation composition for the first adhesive layer.

比較例2Comparative example 2

第一黏著層用的組成物通過混合100重量份的(A1)黏著性樹脂與30重量份的(A4)異氰酸酯類固化劑製備。使用第一黏著層用的製備組成物以與實例1中相同的方式製造偏光板。The composition for the first adhesive layer was prepared by mixing 100 parts by weight of (A1) adhesive resin with 30 parts by weight of (A4) isocyanate-based curing agent. A polarizing plate was produced in the same manner as in Example 1 using the preparation composition for the first adhesive layer.

表1和表2中示出了在實例和比較例中製造的偏光板中的每一個的組分。關於下面的(1)到(5)特性評估第一黏著層、第二黏著層和偏光板,並且表1和表2中示出了結果。The components of each of the polarizing plates manufactured in the examples and the comparative examples are shown in Tables 1 and 2. The first adhesive layer, the second adhesive layer, and the polarizing plate were evaluated regarding the following (1) to (5) characteristics, and the results are shown in Tables 1 and 2.

<表1> <Table 1>

<表2> <Table 2>

如表1和表2中所示,實例的偏光板中的每一個具有第一黏著層的低霧度和高拉伸模數,由此在熱衝擊和高溫/高濕度條件下保持良好的耐久性。因此,本發明提供這樣一種偏光板,該偏光板包含僅僅形成在偏光鏡的一個表面上的保護層,並且在斷裂時或再加工時的惡劣條件下展現出良好的耐久性。本發明提供這樣一種偏光板,該偏光板包含僅僅形成在偏光鏡的一個表面上的保護層,並且在高溫和/或高濕度條件下或在熱衝擊條件下防止偏光鏡中產生開裂和/或偏光鏡的變色。本發明提供這樣一種偏光板,該偏光板包含僅僅形成在偏光鏡的一個表面上的保護層和具有高拉伸模數的黏著層,該黏著層是通過在不使用可熱固化起始劑的情況下的熱固化獲得的。本發明提供這樣一種偏光板,該偏光板包含僅僅形成在偏光鏡的一個表面上的保護層,並且展現出良好的可繞式以用於可繞式顯示器。本發明還提供一種包含本文中闡述的偏光板的光學顯示器。As shown in Tables 1 and 2, each of the example polarizing plates has a low haze and a high tensile modulus of the first adhesive layer, thereby maintaining good durability under thermal shock and high temperature/high humidity conditions. Sex. Accordingly, the present invention provides a polarizing plate comprising a protective layer formed only on one surface of a polarizing mirror, and exhibiting good durability under severe conditions at the time of breaking or reworking. The present invention provides a polarizing plate comprising a protective layer formed only on one surface of a polarizing mirror, and preventing cracking and/or occurrence of cracking in a polarizing mirror under high temperature and/or high humidity conditions or under thermal shock conditions. The discoloration of the polarizer. The present invention provides a polarizing plate comprising a protective layer formed only on one surface of a polarizing mirror and an adhesive layer having a high tensile modulus by using a heat curable initiator In the case of thermal curing obtained. The present invention provides a polarizing plate comprising a protective layer formed only on one surface of a polarizing mirror, and exhibiting a good wrapable type for a wraparound display. The present invention also provides an optical display comprising the polarizing plate set forth herein.

相反,包含玻璃轉化溫度低於50℃的黏著性樹脂的比較例1的偏光板顯現出不佳的耐久性。另外,在並不包含經過脲基甲酸酯基團改性的固化劑的比較例2的偏光板中,第一黏著層和偏光板都顯現出高霧度值。In contrast, the polarizing plate of Comparative Example 1 containing an adhesive resin having a glass transition temperature of less than 50 ° C exhibited poor durability. Further, in the polarizing plate of Comparative Example 2 which did not contain the curing agent modified with the allophanate group, both the first adhesive layer and the polarizing plate exhibited a high haze value.

(1)剝落強度:根據JIS2107相對於玻璃基板在25℃下關於180°剝離強度測量第一黏著層和第二黏著層中的每一個。第一黏著層被切成100毫米×25毫米(長度×寬度)的尺寸,並且層合到玻璃基板上以製備標本。標本的第一黏著層和玻璃基板連接到拉伸測試機(質構分析儀)的上部夾具和下部夾具,隨後在180°的角度下以300毫米/分鐘的拉伸速度從玻璃基板上剝落第一黏著層以測量剝落時的負荷。第二黏著層的剝落強度的測量方法與第一黏著層的剝落強度測量中的方法相同。第二黏著層的剝落強度是平均值,並且由於第二黏著層是軟型黏著層,所以第二黏著層的剝落強度與平均剝落強度可能存在偏差。(1) Exfoliation strength: Each of the first adhesive layer and the second adhesive layer was measured with respect to the glass substrate at 25 ° C with respect to 180° peel strength in accordance with JIS 2107. The first adhesive layer was cut into a size of 100 mm × 25 mm (length × width) and laminated on a glass substrate to prepare a specimen. The first adhesive layer and the glass substrate of the specimen are attached to the upper clamp and the lower clamp of the tensile tester (texture analyzer), and then peeled off from the glass substrate at an angle of 180 mm/min at an angle of 180°. An adhesive layer measures the load at the time of peeling. The method of measuring the peeling strength of the second adhesive layer is the same as that in the measurement of the peeling strength of the first adhesive layer. The peeling strength of the second adhesive layer is an average value, and since the second adhesive layer is a soft adhesive layer, the peeling strength of the second adhesive layer may deviate from the average peeling strength.

(2)拉伸模數:通過根據ASTM D882的應力-應變測試方法在25℃下測量第一黏著層和第二黏著層中的每一個的拉伸模數。第一黏著層用的組成物被塗布在離型薄膜上的預定區域中,並且在90℃下乾燥30分鐘,隨後離型薄膜從標本上去除,由此製備厚度為35微米的第一黏著層。所製備的第一黏著層被切成尺寸為200毫米×5毫米(長度×寬度)的標本。在標本的兩個末端都固定到拉伸測試機的夾具的情況下,在下面的條件下測量拉伸模數。拉伸模數的測量條件如下。(2) Tensile modulus: The tensile modulus of each of the first adhesive layer and the second adhesive layer was measured at 25 ° C by a stress-strain test method according to ASTM D882. The composition for the first adhesive layer was coated on a predetermined region on the release film, and dried at 90 ° C for 30 minutes, and then the release film was removed from the specimen, thereby preparing a first adhesive layer having a thickness of 35 μm. . The prepared first adhesive layer was cut into specimens having a size of 200 mm × 5 mm (length × width). In the case where both ends of the specimen were fixed to the jig of the tensile tester, the tensile modulus was measured under the following conditions. The measurement conditions of the tensile modulus are as follows.

<拉伸模數的測量條件><Measurement conditions of tensile modulus>

測試機:通用測試機(Universal Testing Machine,UTM)Test machine: Universal Testing Machine (UTM)

模型:購自穩定微型系統有限公司(Stable Micro Systems Co., Ltd.)的質構分析儀Model: Texture Analyzer from Stable Micro Systems Co., Ltd.

測量條件:測力計:300牛,拉伸速度:6毫米/秒Measurement conditions: dynamometer: 300 cattle, stretching speed: 6 mm / sec

(3)第一黏著層的霧度:在實例和比較例中製備的第一黏著層用的組成物中的每一種以預定厚度被塗布到離型薄膜上,並且在90℃下乾燥30分鐘,由此製備實例和比較例的第一黏著層中的每一個用的標本。離型薄膜從標本上去除,由此製備第一黏著層。在380奈米到780奈米的波長下使用測霧計(NDH-5000,日本Densuoku有限公司)測量第一黏著層的霧度。(3) Haze of the first adhesive layer: Each of the compositions for the first adhesive layer prepared in the examples and the comparative examples was applied to the release film at a predetermined thickness, and dried at 90 ° C for 30 minutes. Thus, specimens for each of the first adhesive layers of the examples and comparative examples were prepared. The release film is removed from the specimen, thereby preparing a first adhesive layer. The haze of the first adhesive layer was measured using a fog meter (NDH-5000, Densuoku Co., Ltd., Japan) at a wavelength of 380 nm to 780 nm.

(4)偏光板的霧度:在380奈米到780奈米的波長下使用測霧計(NDH-5000,日本Densuoku有限公司)測量實例和比較例的偏光板中的每一個的霧度。(4) Haze of polarizing plate: The haze of each of the polarizing plates of the examples and the comparative examples was measured using a fog meter (NDH-5000, Japan Densuoku Co., Ltd.) at a wavelength of 380 nm to 780 nm.

(5)熱衝擊條件下的耐久性:通過下面的方式製備標本:將尺寸為175毫米×100毫米(長度×寬度)的偏光板層合在玻璃基板上,隨後向偏光板施加4千克到5千克的壓力。標本接受200迴圈的熱衝擊,每個迴圈包含使標本處在-40℃下30分鐘,將標本從-40℃加熱到80℃,並且使標本處在80℃下30分鐘。使標本處在室溫下1小時或更長,並且用肉眼或顯微鏡評估標本。偏光板中未產生開裂或氣泡或者偏光鏡中未產生開裂被評估為○,稍微產生氣泡或開裂或者偏光鏡中稍微產生開裂被評估為△,並且產生嚴重的開裂被評估為×。(5) Durability under thermal shock conditions: Specimens were prepared by laminating a polarizing plate having a size of 175 mm × 100 mm (length × width) on a glass substrate, and then applying 4 kg to 5 to the polarizing plate. Kilograms of pressure. Specimens received 200 cycles of thermal shock, each loop containing the specimen at -40 ° C for 30 minutes, the specimen from -40 ° C to 80 ° C, and the specimen at 80 ° C for 30 minutes. The specimen is allowed to stand at room temperature for 1 hour or longer, and the specimen is evaluated with the naked eye or microscope. No cracking or bubbles were generated in the polarizing plate or no cracking occurred in the polarizing mirror was evaluated as ○, bubble generation or cracking occurred slightly or slight cracking occurred in the polarizing mirror was evaluated as Δ, and severe cracking was evaluated as ×.

(6)高溫/高濕度條件下的耐久性:用與(5)中相同的方法製備標本。使標本處在60℃和95%RH的條件下500小時。使標本處在室溫下1小時或更長,並且用肉眼或顯微鏡評估標本。偏光板中未產生開裂或氣泡被評估為○,稍微產生氣泡或開裂被評估為△,並且產生嚴重開裂被評估為×。(6) Durability under high temperature/high humidity conditions: Specimens were prepared in the same manner as in (5). The specimen was placed under conditions of 60 ° C and 95% RH for 500 hours. The specimen is allowed to stand at room temperature for 1 hour or longer, and the specimen is evaluated with the naked eye or microscope. No cracking or bubble generation in the polarizing plate was evaluated as ○, a slight bubble generation or cracking was evaluated as Δ, and severe cracking was evaluated as ×.

應瞭解,本領域的技術人員可以在不脫離本發明的精神和範圍的情況下作出各種修改、變化、更改以及等效實施例。It will be appreciated that various modifications, changes, variations and equivalents may be made without departing from the spirit and scope of the invention.

10‧‧‧離型薄膜
13‧‧‧第一黏著層用的組成物
13'‧‧‧第一黏著層用的薄片
14‧‧‧第二黏著層用的組成物
14'‧‧‧第二黏著層用的薄片
100‧‧‧偏光板
110‧‧‧偏光鏡
120‧‧‧保護層
130‧‧‧第一黏著層
140‧‧‧第二黏著層
200‧‧‧偏光板
10‧‧‧ release film
13‧‧‧Composition of the first adhesive layer
13'‧‧‧Sheet for the first adhesive layer
14‧‧‧Composition of the second adhesive layer
14'‧‧‧Shelf for the second adhesive layer
100‧‧‧Polar plate
110‧‧‧ polarizer
120‧‧‧Protective layer
130‧‧‧First adhesive layer
140‧‧‧Second Adhesive Layer
200‧‧‧Polar plate

圖1是根據本發明的一個實施例的偏光板的橫截面圖。 圖2是根據本發明的另一個實施例的偏光板的橫截面圖。 圖3是根據本發明的另一個實施例的製造偏光板的方法的流程圖。1 is a cross-sectional view of a polarizing plate in accordance with an embodiment of the present invention. 2 is a cross-sectional view of a polarizing plate in accordance with another embodiment of the present invention. 3 is a flow chart of a method of manufacturing a polarizing plate in accordance with another embodiment of the present invention.

100‧‧‧偏光板 100‧‧‧Polar plate

110‧‧‧偏光鏡 110‧‧‧ polarizer

120‧‧‧保護層 120‧‧‧Protective layer

130‧‧‧第一黏著層 130‧‧‧First adhesive layer

Claims (19)

一種偏光板,其包括: 偏光鏡;以及 第一黏著層,形成於所述偏光鏡的下表面上, 其中所述第一黏著層包括玻璃轉化溫度為50℃或更高的黏著性樹脂,並且所述第一黏著層在380奈米到780奈米的波長下的霧度為1%或更低。A polarizing plate comprising: a polarizer; and a first adhesive layer formed on a lower surface of the polarizer, wherein the first adhesive layer comprises an adhesive resin having a glass transition temperature of 50 ° C or higher, and The first adhesive layer has a haze of 1% or less at a wavelength of from 380 nm to 780 nm. 如申請專利範圍第1項所述的偏光板,其中所述第一黏著層更包括用脲基甲酸酯基團改性後的聚異氰酸酯固化劑。The polarizing plate of claim 1, wherein the first adhesive layer further comprises a polyisocyanate curing agent modified with an allophanate group. 如申請專利範圍第1項所述的偏光板,其更包括: 第二黏著層,其形成於所述第一黏著層的下表面上, 其中所述偏光板在380奈米到780奈米的波長下的霧度為1%或更低。The polarizing plate of claim 1, further comprising: a second adhesive layer formed on a lower surface of the first adhesive layer, wherein the polarizing plate is between 380 nm and 780 nm The haze at the wavelength is 1% or less. 如申請專利範圍第1項所述的偏光板,其中所述偏光鏡的所述下表面受到電暈處理、電漿處理和底塗劑處理中的至少一項處理。The polarizing plate of claim 1, wherein the lower surface of the polarizer is subjected to at least one of a corona treatment, a plasma treatment, and a primer treatment. 如申請專利範圍第1項所述的偏光板,其中所述第一黏著層直接形成於所述偏光鏡的所述下表面上。The polarizing plate of claim 1, wherein the first adhesive layer is directly formed on the lower surface of the polarizer. 如申請專利範圍第1項所述的偏光板,其中所述第一黏著層的拉伸模數根據ASTM D882測量為10兆帕到小於2,000兆帕。The polarizing plate of claim 1, wherein the first adhesive layer has a tensile modulus of 10 MPa to less than 2,000 MPa as measured according to ASTM D882. 如申請專利範圍第3項所述的偏光板,其中所述第二黏著層的拉伸模數根據ASTM D882測量低於所述第一黏著層。The polarizing plate of claim 3, wherein the tensile modulus of the second adhesive layer is lower than the first adhesive layer according to ASTM D882. 如申請專利範圍第2項所述的偏光板,其中用所述脲基甲酸酯基團改性後的所述聚異氰酸酯固化劑的存在量按100重量份的所述黏著性樹脂計為5重量份到50重量份。The polarizing plate according to claim 2, wherein the polyisocyanate curing agent modified with the allophanate group is present in an amount of 5 parts by weight based on 100 parts by weight of the adhesive resin. Parts by weight to 50 parts by weight. 如申請專利範圍第2項所述的偏光板,其中用所述脲基甲酸酯基團改性後的所述聚異氰酸酯固化劑包括用所述脲基甲酸酯基團改性後的四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、十二亞甲基二異氰酸酯和三甲基六亞甲基二異氰酸酯中的至少一種。The polarizing plate of claim 2, wherein the polyisocyanate curing agent modified with the allophanate group comprises four modified with the allophanate group At least one of methylene diisocyanate, hexamethylene diisocyanate, dodecyl diisocyanate, and trimethyl hexamethylene diisocyanate. 如申請專利範圍第1項所述的偏光板,其中所述第一黏著層的厚度為5微米到40微米。The polarizing plate of claim 1, wherein the first adhesive layer has a thickness of 5 micrometers to 40 micrometers. 如申請專利範圍第1項所述的偏光板,其更包括:形成於所述偏光鏡的上表面上的保護層。The polarizing plate of claim 1, further comprising: a protective layer formed on an upper surface of the polarizer. 如申請專利範圍第7項所述的偏光板,其中所述第二黏著層的拉伸模數根據ASTM D882測量為0.01兆帕到小於1兆帕。The polarizing plate of claim 7, wherein the second adhesive layer has a tensile modulus of 0.01 MPa to less than 1 MPa as measured according to ASTM D882. 如申請專利範圍第3項所述的偏光板,其中所述第二黏著層的厚度大於所述第一黏著層。The polarizing plate of claim 3, wherein the second adhesive layer has a thickness greater than the first adhesive layer. 一種偏光板,其包括: 偏光鏡; 第一黏著層,其形成於所述偏光鏡的下表面上;以及 第二黏著層,其形成於所述第一黏著層的下表面上, 其中所述第一黏著層包括玻璃轉化溫度為50℃或更高的黏著性樹脂和用脲基甲酸酯基團改性後的聚異氰酸酯固化劑。A polarizing plate comprising: a polarizer; a first adhesive layer formed on a lower surface of the polarizer; and a second adhesive layer formed on a lower surface of the first adhesive layer, wherein The first adhesive layer includes an adhesive resin having a glass transition temperature of 50 ° C or higher and a polyisocyanate curing agent modified with an allophanate group. 一種製造偏光板的方法,其包括: 同時塗布第二黏著層用的組成物和第一黏著層用的組成物,然後執行乾燥以形成堆疊結構,所述堆疊結構包括所述第一黏著層用的薄片和所述第二黏著層用的薄片; 將所述第一黏著層用的所述薄片與偏光鏡的一個表面層合;以及 固化所述第二黏著層用的所述薄片和所述第一黏著層用的所述薄片。A method of manufacturing a polarizing plate, comprising: simultaneously coating a composition for a second adhesive layer and a composition for a first adhesive layer, and then performing drying to form a stacked structure, the stacked structure including the first adhesive layer a sheet for the second adhesive layer; laminating the sheet for the first adhesive layer with a surface of the polarizer; and curing the sheet for the second adhesive layer and the The sheet for the first adhesive layer. 如申請專利範圍第15項所述的製造偏光板的方法,其中所述堆疊結構包括所述第一黏著層用的所述薄片和依次堆疊在上面的所述第二黏著層用的所述薄片。The method of manufacturing a polarizing plate according to claim 15, wherein the stacked structure includes the sheet for the first adhesive layer and the sheet for the second adhesive layer stacked thereon in sequence . 如申請專利範圍第15項所述的製造偏光板的方法,其中在與所述第一黏著層用的所述薄片層合之前,所述偏光鏡的所述一個表面受到電暈處理、電漿處理和底塗劑處理中的至少一項處理。The method of manufacturing a polarizing plate according to claim 15, wherein the one surface of the polarizer is subjected to corona treatment and plasma before lamination with the sheet for the first adhesive layer. At least one of treatment and primer treatment. 如申請專利範圍第15項所述的製造偏光板的方法,其中所述第一黏著層用的所述組成物包括玻璃轉化溫度為50℃或更高的黏著性樹脂和用脲基甲酸酯基團改性後的聚異氰酸酯固化劑。The method for producing a polarizing plate according to claim 15, wherein the composition for the first adhesive layer comprises an adhesive resin having a glass transition temperature of 50 ° C or higher and an allophanate. The modified polyisocyanate curing agent after the group modification. 一種光學顯示器,其包括如申請專利範圍第1項或第14項所述的偏光板。An optical display comprising the polarizing plate of claim 1 or claim 14.
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